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Polyhedron 26, issue 17, 30 October 2007 www.elsevier.com/locate/poly
Contents Fred Basolo (1920–2007): A tribute from students, colleagues, and family . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4779 Papers Laurent Salles, Jean-Yves Piquemal, Yahdih Mahha, Marion Gentil, Patrick Herson and Jean-Marie Bre´geault Polyhedron 26 (2007) 4786 Crystal structures of three novel dioxotetraperoxodi(molybdenum) heteropolyanions in [PPh4]2[R2SiO2{Mo2O2(l-O2)2(O2)2}] (R2 = (CH3)2, (i-C4H9)2 or (CH3)(CH2Cl)) and characterization of their tungsten analogues
The reaction of MoO3 [or ‘‘WO3 Æ H2O’’], 30 wt% aqueous H2O2 with R2Si(OR0 )2 in alkaline hydrogen peroxide–ethanol affords the dimeric title complexes. These compounds represent a type of silicon-based polyoxoperoxo species which are also obtained by grafting on silica surfaces and in the synthesis of organic/ inorganic mesophases to prepare MOx–SiO2– MCM-41 or MOx–SiO2–SBA-15.
2-
O
O O
O
M
O
O Si
R R
O O
O O
M O O
M = Mo or W R2 = (CH3)2, (i–Bu)2 or (CH3)(CH2Cl) Shen Lin, Ming-Xing Yang and Shi-Xiong Liu Polyhedron 26 (2007) 4793 Three novel trinuclear zinc(II)/nickel(II) complexes with pentadentate ligands N-nitrobenzoylsalicylhydrazidate
Dusˇanka D. Radanovic´, Urszula Rychlewska, Beata War_zajtis, Milica S. Cvijovic´, Mirjana Dj. Dimitrijevic´ and Milosˇ I. Djuran Polyhedron 26 (2007) 4799 Tuning the topologies of Co(II) and Ni(II) complexes with EDTA, 1,3-PDTA and 1,4BDTA ligands: Synthesis and spectroscopic data of [Mg(H2O)6][Co(1,4-bdta)] Æ 3H2O and [Mg(H2O)6][Ni(1,4-bdta)] Æ 3H2O complexes, and the X-ray structure of their chiral crystals
Elsevier Ltd.
Three novel trinuclear complexes Zn3(pnbzshz)2(C5H5N)4 (1), Ni3(p-nbzshz)2(py)4 (2) and Ni3(o-nbshz)2(DMF)2((CH3)2O)2 (3) have been obtained by the reaction of Zn(OAc)2 Æ 4H2O or Ni(OAc)2 Æ H2O with two new ligands, N-p-nitrobenzoylsalicylhydrazidate and N-o-nitrobenzoylsalicylhydrazidate. Complex 1 exhibits a one-dimensional wave-like chain structure resulting from the linkage of the phenolate oxygen donor atoms of the ligand between adjacent trinuclear zinc units. Complex 2 is an uncommon bent trinuclear nickel complex, whilst the three nickel atoms in complex 3 are arranged in a strictly linear fashion.
Stereochemically labile hexadentate cobalt(II) and nickel(II) complexes with 1,4-bdta ligand, [Mg(H2O)6][Co(1,4-bdta)] Æ 3H2O (a) and [Mg(H2O)6][Ni(1,4-bdta)] Æ 3H2O (b), have been synthesized and characterized by UV–Vis spectroscopy and X-ray crystallography. These complexes have been shown to undergo a spontaneous resolution upon crystallization, an unprecedented instance with this type of ligand.
iv
Rupa Shah, Vimal Soni, Aditya Prakash and Raj N. Mehrotra Polyhedron 26 (2007) 4809
Contents
Weak intermediate are involved in the oxidation of SO2 (aq) to SO42) by [ethylenebis(biguanide)]silver(II) in the acidic medium by successive one-electron transfer.
3+
H N
H2N
NH2 C
C
H2C
NH
N Ag
Kinetics and mechanism of oxidation of S(IV) by the ethylenebisbiguanide Ag(III) ion
H2C
N
C
Polyhedron 26 (2007) 4818 Dual-emissive complexes: Visible and nearinfrared luminescence from bis-pyrenyl lanthanide(III) complexes
Noemı´ Andrade-Lo´pez, Jose´ G. Alvarado-Rodrı´guez, Simplicio Gonza´lez-Montiel, Marı´a Guadalupe Rodrı´guez-Me´ndez, Marı´a Elena Pa´ez-Herna´ndez and Carlos Andre´s Gala´n-Vidal Polyhedron 26 (2007) 4825
The syntheses and photophysical attributes of a range of dual-emissive, bis-pyrenyl lanthanide complexes based on a DTPA architecture are described. Irradiation of the pyrene chromophore results in sensitised near-IR emission from NdIII, ErIII and YbIII.
The synthesis and characterization by X ray diffraction, NMR and mass spectrometry of complexes [Pd{(C5H4N)2Y}Cl2] (Y = CNMe, 5; Y = CH(OH), 6 and Y = CH(S2CNEt2), 7) is described. The ligands coordinate to the palladium atom in a bidentate mode. 5 displays a five-membered ring; 6 and 7 display six membered rings.
B. Machura, R. Penczek, R. Kruszynski, J. Kłak, J. Mrozin´ski and J. Kusz Polyhedron 26 (2007) 4833 A novel rhenium(III) complex with bis(pyrazol-1-yl)methane: X-ray structure and DFT calculations for [ReCl3(bpzm)(PPh3)] The [ReCl3(MeCN)(PPh3)2] complex reacts with bis(pyrazol-1-yl)methane (bpzm) to give [ReCl3(bpzm)(PPh3)]. The compound has been studied by IR, UV-Vis spectroscopy and X-ray crystallography. The molecular orbital diagram of [ReCl3(bpzm)(PPh3)] has been calcu-
NH2
NIR emission
O O
O
lated with the density functional theory (DFT) method. The spin-allowed triplet–triplet electronic transitions of [ReCl3(bpzm)(PPh3)] have been calculated with the time-dependent DFT method, and the UV–Vis spectrum of the title compound has been discussed on this basis. The magnetic behavior is characteristic of mononuclear complexes with d4 low-spin octahedral Re(III) complexes (3T1g ground state) and arise because of the large spin–orbit coupling (f = 2500 cm)1), which gives diamagnetic ground state.
N Ln
N O HN
390 nm O
N
337 nm
O O O
NH
Cl
H3C
Cl
Pd
N
N
N
G
N
N Pd
Cl 5
cis-Palladium(II) complexes of derivatives of di-(2-pyridyl)methane: Study of the influence of the bridge group in the coordination mode
Ag(H2L)+ + SO42- + 4H+
C N H
H2N
Simon J.A. Pope
+ SO2(aq)
NH
Cl
6 G= CH(OH) 7 G= CH(S2CNEt2)
Contents
Pradip Kumar Ghosh, Sushanta Saha and Ambikesh Mahapatra Polyhedron 26 (2007) 4841 Pd–Cl cleavage of dichloro-[1-alkyl-2-(naphthylazo)imidazole]palladium(II) complexes by picolinic acid: Kinetic and mechanistic studies
Qing-Feng Xu, Qiu-Xuan Zhou, Jian-Mei Lu, Xue-Wei Xia, Li-Hua Wang and Yong Zhang Polyhedron 26 (2007) 4849 Synthesis, structures and NLO properties of five non-centrosymmetric coordination compounds from the copper(II)/dps system (dps = 4,40 -dipyridyl sulfide)
R. Herna´ndez-Molina, I. Kalinina, P. Esparza, M. Sokolov, J. Gonzalez-Platas, A. Este´vez-Braun and E. Pe´rez-Sacau Polyhedron 26 (2007) 4860 Complexes of Co(II), Ni(II) and Cu(II) with lapachol
v
This work describes kinetics and mechanism of the reaction between picolinic acid (picH) and [Pd(a-/b-NaiR)Cl2] [a-/b-NaiR = 1-alkyl-2(naphthyl-a/b-azo)imidazole] in acetonitrile (MeCN) medium. The product is characterized as [Pd(a/b-NaiR)(pic)](ClO4) by different spectroscopic routes. It is established that the cleavage of Pd–Cl bond is the rate-determining step. Thermodynamic parameters (DH and DS) are determined from variable temperature kinetic studies.
A series of acentric coordination frameworks constructed by Cu(II) and 4,40 -dipyridyl sulfide (dps) were synthesized. All these coordination architectures are generated from achiral building blocks without any chiral auxiliary. The influence of anion and solvent on the structural architecture is discussed. Their second-order NLO properties are also studied.
The complexes of naturally occurring hydroxynaphtho-quinone, lapachol (HL) with Co(II), Ni(II) and Cu(II) have been prepared and the crystal structures of [CoL2(EtOH)2], [NiL2(EtOH)2] and [CuL2(py)2] reported. Characterisation by elemental analyses, cyclic voltammetry and FAB-MS was also performed.
O OH
O
Ann P. Hunter, Anthony M.J. Lees and Andrew W.G. Platt Polyhedron 26 (2007) 4865 Synthesis, structures and mass spectrometry of lanthanide nitrate complexes with tricyclohexylphosphine oxide
Complexes of lanthanide nitrates with tricyclolhexylphosphine oxide show variations in the nitrate coordination as the Ln3+ ionic radii decrease. Tandem mass spectra are simple showing loss of Cy3PO from the complex apart for the Yb complex which undergoes more extensive fragmentation.
O N L
O
O O
L
Er
O N L
O
O
La
N
L
L
O
O
Er
L L
O
O N O
L = Cy3PO
N
O
O O
N O
O O
L
O O
O
Tm
L
N
O
O
O
O
O
O N
O N
N
O
L O
O
O
O L
N O
L O
N
O
vi
Kiran A. Thabaj, Suresh D. Kulkarni, Shivamurti A. Chimatadar and Sharanappa T. Nandibewoor Polyhedron 26 (2007) 4877 Oxidative transformation of ciprofloxacin by alkaline permanganate – A kinetic and mechanistic study
Mei-Lin Ho, Yi-Ming Cheng, Lai-Chin Wu, Pi-Tai Chou, Gene-Hsiang Lee, Fang-Chi Hsu and Yun Chi
Contents
The general scheme is proposed for oxidative transformation of ciprofloxacin, an antibacterial agent by alkaline permanganate to explore the observed experimental results. Products and intermediates were identified by LC-ESIMS/MS technique. Derived rate law consistent with the observed kinetics is Rate ¼
MnO4- + OH[MnO4 OH]
2-
+ Ar N
NH
Complex C
K1 K2 k slow
[MnO4 OH]
2-
Complex (C) +.
Ar N
2-
NH + MnO4
+ OH-
Followed by other fast steps to give products.
kK 1 K 2 ½MnO 4 ½OH ½CF : 1 þ K 1 ½OH þ K 1 K 2 ½OH ½CF
The emission of 1 (2 · 10)5 M in acetonitrile, left) and 1 in the presence of 4 · 10)6 M solution of Pb2+ excited at 365 nm (UV lamp).
Polyhedron 26 (2007) 4886 Probing Pb2+ cation via the iridium based phosphorescent dye
Ilia Sokka, Andreas Fischer and Lars Kloo Polyhedron 26 (2007) 4893 Optimization of the synthesis of non-symmetrical alkyl dimethyl sulfonium halides
Sergey N. Semenov, Andrey Yu. Rogachev, Svetlana V. Eliseeva, Yury A. Belousov, Andrey A. Drozdov and Sergey I. Troyanov Polyhedron 26 (2007) 4899 5-Nitroaminotetrazole as a building block for extended network structures: Syntheses and crystal structures of a number of heavy metal derivatives
A high-yield, one-step synthesis of sulfonium halogenides with long alkyl chains is described. A polar electrophilic solvent, trifluoroacetic acid, was used as reaction medium. Dodecyl dimethyl sulfonium, hexadecyl dimethyl sulfonium bromides and chlorides of high purity were obtained and characterized. The crystal structure of hexadecyl dimethyl sulfonium bromide has been determined.
Two extended network structures with the formulas [Pb(CHN6O2)2(H2O)4]n and [Hg(CN6O2)(H2O)2]n were obtained from 5nitroaminotetrazole, both complexes were characterized by X-ray crystallography. The influence of chemical hardness and charge distribution on the reactivity and coordination properties of 5-nitroaminotetrazole have been estimated based on density functional calculations.
Alk-X + S
CF3COOH
Alk
Alk = n-CH3(CH2)10CH2-, n-CH3(CH2)14CH2X = Cl, Br
S
X-
Contents
Vahid Amani, Nasser Safari, Hamid Reza Khavasi and Peiman Mirzaei Polyhedron 26 (2007) 4908 Iron(III) mixed-ligand complexes: Synthesis, characterization and crystal structure determination of iron(III) hetero-ligand complexes containing 1,10-phenanthroline, 2,20 -bipyridine, chloride and dimethyl sulfoxide, [Fe(phen)Cl3(DMSO)] and [Fe(bipy)Cl3(DMSO)]
Hsi-Ying Hsieh, Ching-Wen Cheng, Fuh-An Yang, Jyh-Horung Chen, Jo-Yu Tung, Shin-Shin Wang and Lian-Pin Hwang Polyhedron 26 (2007) 4915 The structures of (phenylato)(N-2-thiophenecarboxamido-meso-tetraphenylporphyrinato)mercury(II) and bisphenylmercury(II) complex of 21-(4-tert-butyl-benzenesulfonamido)5,10,15,20-tetraphenylporphyrin
Subal Chandra Manna, Joan Ribas, Ennio Zangrando and Nirmalendu Ray Chaudhuri Polyhedron 26 (2007) 4923 Dipyridyl bridged coordination polymers of Cu(II): Synthesis, crystal structure and magnetic study
Elena Ioachim, Elaine A. Medlycott, W.G. Skene and Garry S. Hanan Polyhedron 26 (2007) 4929 Synthesis and properties of 6,60 -dithienyl-4,40 bipyrimidine and its hetero- and homo-leptic Ru(II) complexes
[Fe(bipy)Cl3(DMSO)] and [Fe(phen)Cl3(DMSO)] complexes (where bipy is 2,20 -bipyridine, phen is 1,10-phenanthroline and DMSO is dimethyl sulfoxide) were prepared and characterized by elemental analysis, IR, UV–Vis and 1H NMR spectroscopies and by the X-ray diffraction method.
We have investigated two new diamagnetic porphyrin complexes, namely, mononuclear mercury(II) complex of 6 Æ CH2Cl2 Æ 0.5C6H14 and dinuclear mercury(II) complex of 7, and their X-ray structures are established.These two porphyrins complexes are of SAT type. The tetracoordination for the Hg(1) in 6 Æ CH2Cl2 Æ 0.5C6H14 and Hg(2) in 7 is demonstrated and a linear coordination is described for the Hg(1) in 7.
Coordination polymers, [Cu(bpp)(H2O)2(ClO4)2]n (1) and {[Cu(bpds)2(ClO4)2] Æ 1.5(H2O)}n (2) [bpp, 1,3-bis(4-pyridyl)propane and bpds, 4,40 -bipyridyl disulfide] have been synthesized and characterized by X-ray single crystal diffraction study and magnetic measurement.
A new bis(thienyl)-bipyrimidine ligand readily forms Ru(II) complexes which emit at significantly lower energy than the parent Ru(bpy)32+ complex.
vii
[Fe(N-N)Cl4][N-N.H]
CH3OH/DMSO
N-N is bipyridine and phenanthroline
[Fe(N-N)Cl3(DMSO)] + N-N. HCl
viii
Marco Bortoluzzi, Emilio Bordignon, Gino Paolucci and Bruno Pitteri Polyhedron 26 (2007) 4936 A computational study on mixed-ligand N2P3 donor-set iron(II) and ruthenium(II) classical and non-classical hydrides
Andrei S. Zelenev, Josepha M. Fu and Bruce A. Keiser Polyhedron 26 (2007) 4941 Establishing the difference between colloidal borosilicate and boron-modified colloidal silica via chelation of boron with catechol and D L -tartaric acid
Teresa F. Mastropietro, Donatella Armentano, Nadia Marino and Giovanni De Munno Polyhedron 26 (2007) 4945 Metal–nucleobase interactions in magnesium(II) and manganese(II) complexes with adenine: Influence of the anion on the noncovalent stabilization of 7H-adenine tautomer
Matthew C. Hales and Ray L. Frost Polyhedron 26 (2007) 4955 Synthesis and vibrational spectroscopic characterisation of synthetic hydrozincite and smithsonite
Contents
The results of DFT calculations on hydride complexes of the type [MH(N–N)P3]+ and [M(g2-H2)(N–N)P3]2+ {M = Fe, Ru; N–N = 2,20 -bipyridine (bpy), 1,10-phenanthroline (phen); P = PH3, PF3}, are described. A good correlation between various computed molecular properties and experimental data reported in the literature is highlighted. The charge distributions obtained from DFT calculations allow to hypothesize that the different acidities of iron and ruthenium nonclassical hydrides could be mainly justified on the basis of the difference of electronegativity of the two metal ions considered.
Colloidal borosilicate and boron-modified colloidal silica sols both contain B–O–Si chemical bonds that can be detected by 11B NMR. While the boron present in colloidal borosilicate is stable towards the action of catechol and tartaric acid, the boron in boronmodified silica is readily complexed by these agents.
The synthesis and crystal structure of the compounds [Mg(H2O)6X2 Æ 2ade] (with X = Cl) (1), Br) (2), ClO4) (3)), [Mn(H2O)4 Æ (ade)2 Æ (ClO4)2] (4), and [Mn2(H2O)6 Æ (ade)2 Æ (NO3)4 Æ 2H2O] (5) (where ade = adenine) are reported. Compounds 1–3 consist of self-assembled hexaaquo Mg(II) ions, ade molecules and anions. Compounds 4 and 5 represent a rare example of direct Mn–N binding involving isolated nucleobases and the first one containing ade as ligand. The detailed analysis of non-covalent interactions in all the compounds prove that the anions play a crucial role in determining the non-covalent stabilization of the minor 7Hadenine tautomer.
Hydrozincite and smithsonite were synthesised by controlling the partial pressure of CO2 resulting from the reaction in solution of zinc chloride and sodium bicarbonate. Raman spectroscopy complimented with infrared spectroscopy has been used to characterise the vibrational spectra of these synthesised minerals.
Contents
Hamid Khanmohammadi, Razyeh Arabahmadi, Mohammad H. Abnosi and Hamid R. Khavasi Polyhedron 26 (2007) 4963 Synthesis, crystal structure, spectral and biological studies of CuII–MII(M = Zn and Pb) heterodinuclear complexes of new phenolbased macrocyclic ligands
Subrata Patra, Eringathodi Suresh and Parimal Paul Polyhedron 26 (2007) 4971 Functionalized calix[4]arene as an ionophore: Synthesis, crystal structures and complexation study with Na+ and K+ ions
ix
A series of heterodinuclear Cu(II)–M(II) (M = Pb and Zn) complexes of new phenolbased compartmental macrocyclic ligands, possessing contiguous (N2O2) and (NxO2) (x = 2, 3) coordination sites, was prepared and their biological activity has been tested in vitro. The crystal structure of [CuZn L3(H2O)](ClO4)2 was determined by X-ray diffraction and shows that the Zn(II) and Cu(II) centres reside in the N2O2 sites of the macrocyclic ligand.
A family of trisubstituted calix[4]arenes with a partial cone conformation has been synthesized and structurally characterized. Crystal structural analyses show that the precise shape of the molecule, and intra- and intermolecular interactions (C–H p, p p and C–H O) of these compounds are significantly different due to the variation of the substituents. A complexation study with Na+ and K+ ions reveal that one of the ionophores (L3) selectively forms a complex with the latter ion.
OR
O
OR
OH
OH2 Cl
K+
O
Cl
O
OH2 O
OH OR
OR
R = -C H 2C H 2C H 3
Li-Ying Wang, Quan-Ling Suo, Li-Min Han, Yi-Bing Wang and Lin-Hong Weng Polyhedron 26 (2007) 4981 Synthesis and structural characterization of new p-ferrocenylphenylacetylene bridged cobalt carbonyl clusters
Zheng-Xing Zhang, Yan-Rong Li, Rui-Ting Liu, Zhen-Xia Chen, Lin-Hong Weng and Xi-Geng Zhou Polyhedron 26 (2007) 4986 Insertion reaction of elemental sulfur into the Ln–C bond: Synthesis and characterization of [(C5H4SiMe2tBu)2Ln(l-SR)]2 (R = Me, Ln = Yb, Er, Dy, Y; R = nBu, Ln = Yb, Dy)
A new ferrocenylphenyl butadiynyl compound L and three new complexes 1, 2 and 3 have been synthesized. The composition and structure of the four compounds were characterized by elemental analysis, FTIR, NMR and MS. The molecular and crystal structures of L and 2 were analyzed by X-ray single crystal diffraction.
Treatment of (C5H4SiMe2tBu)2LnR with elemental sulfur leads to the formation of dimeric complexes [(C5H4SiMe2tBu)2Ln(l-SR)]2 [R = Me, Ln = Yb, Er, Dy, Y; R = nBu, Ln = Yb, Dy], providing a new route to the syntheses of lanthanocene thiolates.
(C 5H 4SiMe 2tBu)2 LnR
1/8 S8 toluene, rt
[(C5 H4 SiMe2 tBu)2 Ln(μ − SR)]2
R = Me, Ln = Yb, Er, Dy, Y; R = nBu, Ln = Yb, Dy
x
Tarlok S. Lobana, Gagandeep Bawa, Geeta Hundal, A.P.S. Pannu, Ray J. Butcher, Ben-Jie Liaw and Chen W. Liu Polyhedron 26 (2007) 4993 The influence of substituents (R) at the C2 carbon on bonding properties of thiosemicarbazones {RC2(H)@N3-N2H–C1(@S)–N1H2} in palladium(II) complexes Reactions of the PdCl2(PPh3)2 precursor with furan-2-carbaldehyde thiosemicarbazone (Hftsc) and thiophene-2-carbaldehyde thiosemicarbazone (Httsc), in 1:1 molar ratios in the presence of Et3N base, removed one Cl and
Ricardo C. Santana, Jesiel F. Carvalho, Ivo Vencato, Hamilton B. Napolitano, Adailton J. Bortoluzzi, Gasto´n E. Barberis, Raul E. Rapp, Mario C.G. Passeggi and Rafael Calvo Polyhedron 26 (2007) 5001 Synthesis, crystal structure and magnetic properties of a new dinuclear copper(II) amino acid complex [Cu2(L -arg)2(l-HPO4-O)(l-HPO4O,O0 )(l-OH)]) Æ (H3O)+ Æ (H2O)6
Joaquı´n Borra´s, Gloria Alzuet, ´ lvarez, Francisco Estevan, Marta Gonza´lez-A Benigno Macı´as, Malva Liu-Gonza´lez and Alfonso Castin˜eiras Polyhedron 26 (2007) 5009 Crystal structures and spectroscopic properties of copper(II)–bis(2-pyridylcarbonyl)amide– chlorobenzoate complexes
P.N. Remya, C.H. Suresh and M.L.P. Reddy Polyhedron 26 (2007) 5016 Rapid reduction and complexation of vanadium by 1-phenyl-3-methyl-4-toluoyl-5-pyrazolone: Spectroscopic characterization and structure modelling
Contents
one PPh3 group from the PdII center, and yielded the complexes, [Pd(g2-N3,S-ftsc)(PPh3)Cl] (1) and [Pd(g2-N3,S-ttsc)(PPh3)Cl] (2), respectively, However, when a 1:2 molar ratio (M:L) was used, both the Cl and PPh3 ligands were removed, yielding complexes, [Pd(g2-N3,S-ftsc)2] (3) and [Pd(g2-N3,S-ttsc)2] (4). In contrast, reactions with pyrrole-2-carbaldehyde thiosemicarbazone, (H2ptsc) and salicylaldehyde thiosemicarbazone, (H2stsc) in 1:1 or 1:2 molar ratios have invariably formed the complexes [Pd(g3-N4,N3,S-ptsc)(PPh3)] (5) and [Pd(g3–O,N3,S-stsc)(PPh3)] (6), respectively.
The synthesis, characterization and crystal structure of a novel dinuclear copper compound with L -arginine, mono and bidentate HPO42) oxoanions and an OH) anion are reported. The dinuclear character and bridging scheme, rare for metal–amino acid compounds, is attributed to the bonding characteristic of the phosphate anions. The magnetic properties and EPR spectra indicate an antiferromagnetic intradinuclear interaction J/kB = )3.7 K and a ferromagnetic coupling between these dinuclear units of J0 /kB 0.3 K.
The reaction of 2,4,6-tris(pyridyl)-1,3,5-triazine (ptz) and copper(II) salts in DMF–water resulted in the hydrolysis of ptz, giving rise to the bis(2-pyridylcarbonyl)amide anion (ptO2)) and affording the complexes [Cu(ptO2)(2Clbenz)(H2O)], [Cu(ptO2)(3-Clbenz)], and [Cu(ptO2)(4-Clbenz)(DMF)]. This report includes the chemical, the spectroscopic characterization and the crystal structures of all these compounds.
The reduction of vanadium(V) by 1-phenyl-3methyl-4-toluoyl-5-pyrazolone over the pH range of 1.0–7.0 has been assessed by various spectroscopic techniques. The reaction proceeds by the transfer of one electron to vanadium(V) by the ligand via the formation of a free-radical intermediate, and subsequently the reduced vanadium species rapidly complexes with the available free ligand and forms vanadyl complex. These reduction reactions occur under physiological conditions and thus could be important to the reduction of vanadium(V)-containing coordination compounds used as insulin-enhancing agents for treatment of diabetics.
Contents
Habibar Chowdhury, Rajarshi Ghosh, Sk. Hafijur Rahaman and Barindra Kumar Ghosh Polyhedron 26 (2007) 5023 Syntheses, X-ray structures and properties of a dinuclear cadmium(II)azido and a polymeric cadmium(II)thiocyanato compounds containing bis(tridentate) congregators One-pot reactions of cadmium(II) perchlorate/ nitrate, Schiff bases (pbap/pfap) and pseudohalides (sodium azide/ammonium thiocyanate) in a 2:1:4 molar ratio in MeOH–MeCN solvent mixtures at room temperature result in a di-
Alina Bien´ko, Julia Kłak, Jerzy Mrozin´ski, Sławomir Domagała, Bohdan Korybut-Daszkiewicz and Krzysztof Woz´niak Polyhedron 26 (2007) 5030 Magnetism and crystal structures of CuIIMnII and CuIINiII ordered bimetallic chains The syntheses, crystal structures and magnetic properties of the new bimetallic compounds {CuLa[Ni(NCS)4(H2O)2]} (1) and {CuLa[Mn(NCS)4(H2O)2]} (2), where L = N-dl-5,12-dimethyl-1,4,8,11tetraazacyclotetradeca-4,11-diene, are reported. Both structures consist of well-separated and magnetically equivalent layers which are composed of thiocyanate-
Padavattan Govindaswamy, Yurij A. Mozharivskyj and Mohan Rao Kollipara Polyhedron 26 (2007) 5039 New pentamethylcyclopentadienyl rhodium and iridium complexes containing arylazoimidazole ligands: Crystal and molecular structure of the complex [(g5-C5Me5)RhCl(Me– C6H4–N@N–C3H3N2)]+
Tamara V. Basova, Ays¸e G. Gu¨rek, Devrim Atilla, Aseel K. Hassan and Vefa Ahsen Polyhedron 26 (2007) 5045 Synthesis and characterization of new mesomorphic octakis(alkylthio)-substituted lead phthalocyanines and their films
nuclear compound [Cd2(pbap)(OH2)2(N3)4] (1) [pbap = N-(1-pyridin-2-ylbenzylidene)-N-[2(4-{2-[(1-pyridin-2-ylbenzylidene)amino]ethyl}piperazin-1-yl)ethyl]amine] and a polymeric compound [Cd2(pfap)(l1,3-NCS)(l1,3SCN) (NCS)2]n (2) [pfap = N-(1-pyridin-2ylformylidene)-N-[2-(4-{2-[(1-pyridin-2ylformylidene) amino]ethyl}piperazin-1-yl)ethyl]amine]. X-ray crystal structural analyses reveal a bis (tridentate) congregation behaviour of the hexadentate blocker (pbap/pfap) encapsulating two metal centers. Both the complexes display intraligand 1(p–p*) fluorescence and intraligand 3(p–p*) phosphorescence in glassy solutions.
bridged Cu(II)–Mn(II) or Cu(II)–Ni(II) binuclear units and create infinite polymeric zig-zag-like chains in the crystal lattices. The [Ni(NCS)4(H2O)2] and [Mn(NCS)4(H2O)2] molecular fragments have a distorted octahedral symmetry. The geometry of the Cu(II) unit is octahedral with the apical positions occupied by bridging thiocyanate ligands and the basal ones by four nitrogen atoms from the macrocyclic ring. The shortest intramolecular M–M dis˚ (Cu–Ni) and 6.421 A ˚ (Cu–Mn). tances are: 6.342 A Magnetic susceptibility and magnetization measurements for the examined compounds have been carried out over the range 1.8–300 K. The data suggest antiferromagnetic interactions through the thiocyanate bridge. Finally, the magnitudes of the Cu(II)– M(II) interactions (M = Ni and Mn) have been compared and qualitatively rationalised.
The dimeric complexes [{(g5-C5Me5)M(lCl)Cl}2] where M = Rh and Ir reacts with several arylazoimidazole (RaaiR0 ) ligands to give the mononuclear cationic complexes of the type [(g5-C5Me5)MCl(RaaiR0 )]+. The molecular structure of the complex [(g5-C5Me5)RhCl(Me–C6H4–N@N–C3H3N2)]+ 4[PF6] was established by single crystal X-ray diffraction study.
The syntheses of new octakis (alkylthio)-substituted phthalocyanines of Pb(II) (1a and 2a) are described. These phthalocyanine derivatives are liquid at room temperature and form columnar-hexagonal (Colh) mesophases below )10 C. Thin films of octakis(alkylthio)-substituted Pb(II) phthalocyanines 1a and 2a were prepared by the method of spin-coating.
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Qing Su, Qiao-Lin Wu, Guang-Hua Li, Xiao-Ming Liu and Ying Mu Polyhedron 26 (2007) 5053 Bis-salicylaldiminato zinc complexes: Syntheses, characterization and luminescent properties Bis-salicylaldiminato zinc complexes with four new salicylaldiminato ligands: (Ar1 = 7-(2,4-Me2) (Ar1N=HCAr2O)2Zn C9H4N, Ar2 = C6H4 (2a); Ar1 = 7-(2,4-Me2)
Susobhan Biswas, Saikat Sarkar, Ian M. Steele, Sougata Sarkar, Golam Mostafa, Bijali Bikash Bhaumik and Kamalendu Dey Polyhedron 26 (2007) 5061 Two-dimensional supramolecular assembly of phenylmercury(II) and cadmium(II) complexes with a tridentate thiohydrazone NNS donor ligand: Synthesis, coordination behavior and crystal structure
Raif Kurtaran, Sinem Odabas¸ıog˘lu, Akin Azizoglu, Hu¨lya Kara and Orhan Atakol Polyhedron 26 (2007) 5069 Experimental and computational study on [2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine] (dithiocyanato)mercury(II) The mercury complex of 2,6-bis(3,5-dimethylN-pyrazolyl)pyridine (bdmpp) has been synthesized and characterized by X-ray diffraction, IR, UV–Vis and TGA–DTA methods. The structure consists of units in which the
Jeanet Conradie, Gert J. Lamprecht, Andreas Roodt and Jannie C. Swarts Polyhedron 26 (2007) 5075 Kinetic study of the oxidative addition reaction between methyl iodide and [Rh(FcCOCHCOCF3)(CO)(PPh3)]: Structure of [Rh(FcCOCHCOCF3)(CO)(PPh3)(CH3)(I)]
Contents
C9H4N, Ar2 = 3,5-tBu2C6H2 (2b); Ar1 = 7(2,4-Me2)C9H4N, Ar2 = 5-BrC6H3 (2c); Ar1 = 7-(2,4-Me2)C9H4N, Ar2 = 3,5-Br2C6H2 (2d)) have been synthesized and characterized by elemental analyses, 1H, 13C NMR and IR spectroscopy.The molecular structure of complex 2b was confirmed by X-ray crystallography, showing intermolecular p–p interactions in the solid state.These complexes produce bright fluorescence in both solution and the solid state. In addition, the emission color in solution can be tuned in the range 503–532 nm by the modification of the salicylaldiminato ligand.
The reaction of diacetylmonoxime and morpholine N-thiohydrazide with phenylmercury(II) acetate and cadmium(II) acetate formed the novel phenylmercury(II) complex, [PhHg(Hdammthiol)] (1) and the cadmium(II) complex, [Cd(Hdammthiol)2] (2), respectively (where H2dammthiol is the thiol form of diacetylmonoximemorpholine N-thiohydrazone (Hdammth)). Both complexes form two-dimensional supramolecular sheet and a new non-conventional CH3 O interaction (in cadmium complex).
mercury atom is a penta-coordinated by two sulfur and three nitrogen atoms. [Hg(bdmpp)(SCN)2] has a distorted square pyramidal geometry. The optimized geometry at both PM3 and DFT methods agrees with the X-ray structure well. The infrared spectra of the title complex was studied in the 4000– 400 cm)1 frequency range experimentally and theoretically. The experimental results are in better agreement with the DFT results at the B3LYP/LanL2DZ level than the semi-empirical results at the PM3 level.
The chemical kinetics, studied by UV/Vis, IR, H and 31P NMR techniques, of oxidative addition of CH3I to [Rh(FcCOCHCOCF3)(CO)(PPh3)] with Fc = ferrocenyl, consist of three definite sets of reactions and involves geometrical isomers of two different RhIIIalkyl and two different RhIII-acyl species. 1
F3C
F3C Rh O
CO
PPh3 CO Rh O CH3 O
PPh3
O
CH 3 I
I
Fe
Fe
Kc F3C
H3C CO
O
Rh
PPh3
Fe
Rh(I) isomers
PPh3
O
Rh O
O
C
F3C O
I
Fe
+ other geometrical isomers
Contents
P.F. Rapheal, E. Manoj and M.R. Prathapachandra Kurup Polyhedron 26 (2007) 5088 Syntheses and EPR spectral studies of manganese(II) complexes derived from pyridine-2carbaldehyde based N(4)-substituted thiosemicarbazones: Crystal structure of one complex Five manganese(II) complexes {½MnL1 2 H2 O EtOH, [Mn(L1)(HL1)]OAc, ½MnL1 2 3H2 O, ½MnL1 2 3H2 O and [Mn(HL3)2](SCN)2 Æ MeOH} of three NNS donor N(4)-
Timothy J. Boyle, Harry D. Pratt III, Todd M. Alam, Mark A. Rodriguez and Paul G. Clem Polyhedron 26 (2007) 5095 Synthesis and characterization of solvated trifluoroacetate alkaline earth derivatives
Subhra Basak, Soma Sen, Sambuddha Banerjee, Samiran Mitra, Georgina Rosair and M.T. Garland Rodriguez Polyhedron 26 (2007) 5104 Three new pseudohalide bridged dinuclear Zn(II) Schiff base complexes: Synthesis, crystal structures and fluorescence studies
Kjell Ove Kongshaug and Helmer Fjellva˚g Polyhedron 26 (2007) 5113 Syntheses, structures and magnetic properties of Mn(II) containing 3D polymeric networks
substituted thiosemicarbazone ligands {pyridine-2-carbaldehyde N(4)-p-methoxyphenyl thiosemicarbazone [HL1], pyridine-2carbaldehyde N(4)-2-phenethylthiosemicarbazone [HL2] and pyridine-2-carbaldehyde N(4)-methyl, N(4)-phenyl thiosemicarbazone [HL3]} were synthesized and physico-chemically characterized. The crystal structure of the compound ½MnL1 2 H2 O has been determined by X-ray diffraction studies. It is found to have a distorted octahedral geometry. EPR spectra in DMF solutions at 77 K show hyperfine sextets with low intensity forbidden lines lying between each of the two main hyperfine lines.
A series of alkaline earth trifluoracetic acid (TFA) derivatives were crystallographically characterized as: Mg(TFA)2(py)4 (1), {[Ca2(lTFA)3(THF)4](l-TFA)}n (2), {[(l-TFA)2Sr(lc-TFA)][H-py]py}n(3); and {[Ba(lc-TFA)2(lc-TFA)(py)][H-py]}n (4) (shown). Elemental analyses, solid-state, and solution multinuclear NMR, and FTIR data confirms the bulk powders were consistent with the X-ray structures.
Three new dinuclear Zn(II) complexes [Zn(L)(l1,1-N3)Zn(L)(N3)] Æ 1.5H2O (1), [Zn(L)(l1,1-NCO)Zn(L)(NCO)] Æ 1.5H2O (2) and [Zn(L)(l1,1-NCS)Zn(L)(NCS)(OH2)] (3) of the Schiff base ligand LH [LH = (OCH3)(OH)C6H3CHN(CH2)2N(CH3)2] have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, TGA, fluorescence and single crystal X-ray diffraction studies. All the synthesized complexes display intraligand 1(p–p*) fluorescence and can serve as potential photoactive materials.
Two novel coordination polymers based on Mn(II) have been prepared, and their crystal structures have been solved by single crystal Xray diffraction. Thermal and magnetic properties are discussed.
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xiv
J.G. Małecki, R. Kruszyn´ski, D. Tabak and J. Kusz Polyhedron 26 (2007) 5120 The reactions between [RuHCl(CO)(PPh3)3] and quinoline carboxylic acids The reactions of [RuHCl(CO)(PPh3)3] with 8hydroxy-2-methyl-quinoline-7-carboxylic acid and quinoline-2-carboxylic acid have been examined, and two novel ruthenium(II) complexes – [(PPh3)2RuH(CO)(C10H8NO3)] and [(PPh3)2RuCl(CO)(C9H6O2)] – have been obtained. The compounds have been studied by
Ramesh Kapoor, Ashok Kataria, Pratibha Kapoor, Ajay Pal Singh Pannu, Maninder Singh Hundal and Montserrat Corbella Polyhedron 26 (2007) 5131 Synthesis, X-ray structure and magnetic studies of Cu(II) complexes of tridentate SNS ligands (S-dbpt, N,N,N0 ,N0 -tetraisobutylpyridine-2,6-dithiocarboxamide; S-dppt, N,N, N0 ,N0 -tetraisopropylpyridine-2,6-dithiocarboxamide): Role of steric factors on the geometry around Cu(II)
Joy Chakraborty, Santarupa Thakurta, Brajagopal Samanta, Aurkie Ray, G. Pilet, Stuart R. Batten, Paul Jensen and Samiran Mitra Polyhedron 26 (2007) 5139 Synthesis, characterisation and crystal structures of three trinuclear cadmium(II) complexes with multidentate Schiff base ligands Three novel trimeric Cd(II) complexes have been prepared from two different symmetrical Schiff bases. Crystal structures of all the complexes have been established by single crystal
Marisa Belicchi-Ferrari, Franco Bisceglie, Giorgio Pelosi, Silvana Pinelli and Pieralberto Tarasconi Polyhedron 26 (2007) 5150 Synthesis, characterization, crystal structure and antiproliferative in vitro activity of longchain aliphatic thiosemicarbazones and their Ni(II) complexes
Contents
IR and UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagrams of the complexes have been calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of the compounds have been calculated with the time-dependent DFT method, and the UV–Vis spectra of the compounds have been discussed on this basis.
HOOC
N
Cl
CH3
O Ph3P
N
Ru
Ru
PPh3 C
H
CO
CO
PPh3 PPh3
O
O
Two new tetranuclear copper(II) complexes, each formed by a cationic and an anionic dinuclear species are reported. Both of them, characterized by X-ray diffraction, show the same anionic complex [{CuCl2}2(l-Cl)2]2) which shows weak antiferromagnetic coupling. The dinuclear cationic species [{Cu(S-dbpt)}2(l-Cl)2]2+ shows ferromagnetic behaviour.
X-ray diffraction methods. The ligands and their metal complexes have been characterised by analytical and spectroscopic techniques. Among the three complexes, 1 and 3 are linear whereas 2 is a cyclic trimer. In 1 and 3, all the doubly phenoxo bridged Cd(II) metal centres have a distorted octahedral environment. In the complex 2, two out of the three Cd(II) centres reside in a distorted octahedral environment and the remaining one enjoys a monocapped octahedral geometry. Altogether a variety in the bridging mode of two new salen-type ligands has been established.
Nine long-chain aliphatic thiosemicarbazones and their nickel complexes were prepared and characterized by spectroscopic methods and for five of the complexes also by X-ray crystallography diffraction analysis. Heptanal thiosemicarbazone and the corresponding nickel complex were chosen after a solubility/ stability test to carry out preliminary experiments in vitro on human leukemia cell line U937. The complex possesses a remarkable biological activity in inhibiting cell growth and in inducing apoptosis.
N1 N2 S1
C3
C1 N3
C4 C2
Ni1
C6
C5 C7
C8
Contents
ˇ eljka Soldin, Gordana Pavlovic´, Z Zora Popovic´ and Vesna Tralic´-Kulenovic´ Polyhedron 26 (2007) 5162 Synthesis and characterization of mercury(II) complexes with 2-styryl-1,3-benzothiazole (sb). Presence of two differently coordinated Hg(II) ions in the dinuclear complex Hg2Cl4(sb)3. Structural characterization of 2-styryl-1,3-benzothiazole and some of its derivatives
Hui Wang, Ming-Xing Li, Min Shao and Xiang He Polyhedron 26 (2007) 5171 Syntheses, structures and luminescent properties of four copper(I) cyanide coordination polymers based on 2-(n-pyridyl)benzimidazole ligands (n = 2,3,4)
Kou-Lin Zhang, Hong-Yan Gao, Zi-Cai Pan, Wei Liang and Guo-Wang Diao Polyhedron 26 (2007) 5177 Preparation and characterization of two threedimensional metal–organic photoluminescent supramolecular networks Two novel photoluminescent coordination compounds of the formula [Cd(atpt)phen(H2O)] Æ H2O (1) and [Zn2(atpt)2(bipy)2(H2O)2] (2) (H2atpt = 2aminoterephthalic acid, bipy = 2,20 -bipyridine and phen = 1,10-phenanthroline) were synthesized through the self-assembly of H2atpt and N-containing ligands (bipy for 1 and phen for 2) with metal(II)
Laure Latapie, Julien Le Gal, Bassem Hamaoui, Joe¨l Jaud, Marie Gressier and Eric Benoist Polyhedron 26 (2007) 5185 First examples of neutral rhenium(V) complexes with a novel semi-rigid ligand containing a P,N,N,S donor atom set: Synthesis, characterisation and crystal structure
Mercury(II) chloride and bromide form two novel complexes 2 and 5 with 2-styryl-1,3benzothiazole (sb). Compounds with different nuclearities were obtained under identical reaction conditions (ethanol medium, 1:2 molar ratio). The structure of 2 consists of dinuclear Hg2Cl4(sb)3 units and compound 5 of monomeric HgBr2(sb)2 units.
Four copper(I) cyanide coordination polymers containing 2-(n-pyridyl)benzimidazole ligands were synthesized. They possess one-dimensional linear chain, ladder-like double chain, saddle-shaped helical chain, and two-dimensional layer polymeric structures.
ions in the presence of NaOH, and characterized by FT-IR spectroscopy, thermogravimetric analysis (TG), X-ray analysis and photoluminescence spectra in the solid state. The coordination mode of the atpt ligand in 2 is novel and is first reported in this presentation. Compound 1 shows a 1D architecture and further assembles into a 3D supramolecular network via interchain hydrogen bonds and p–p stacking interactions. Compound 2 exhibits a binuclear structure with intramolecular p–p stacking interactions, which is further extended into a 3D supramolecular framework via intermolecular hydrogen bonds and C–H p interactions. Compounds 1 and 2 exhibit green photoluminescence in the solid state at room temperature.
The synthesis of a novel PN2S-tetradentate ligand [Ph-P(Ph2)N2S(Trt)] (2) and its metal complexation with ReV precursors have been studied. Whilst the reaction of 2 with ReOCl3(PPh3)2 gave the expected stable complex [ReO{Ph-P(Ph2)N2S}] (4), an unexpected neutral and diamagnetic species, [ReN{PhP(Ph2)N2S(Trt)}] (5), has been isolated during the complexation of 2 with ReNCl2(PPh3)2.
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Contents
Corrigendum to ‘‘Structural diversities and spectroscopic properties of bis and tris (1,10-phenanthroline)copper(II) complexes’’ [Polyhedron 26 (2007) 1459–1468] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5191
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Polyhedron 26, issue 17, 30 October 2007 www.elsevier.com/locate/poly
Contents Fred Basolo (1920–2007): A tribute from students, colleagues, and family . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4779 Papers Laurent Salles, Jean-Yves Piquemal, Yahdih Mahha, Marion Gentil, Patrick Herson and Jean-Marie Bre´geault Polyhedron 26 (2007) 4786 Crystal structures of three novel dioxotetraperoxodi(molybdenum) heteropolyanions in [PPh4]2[R2SiO2{Mo2O2(l-O2)2(O2)2}] (R2 = (CH3)2, (i-C4H9)2 or (CH3)(CH2Cl)) and characterization of their tungsten analogues
The reaction of MoO3 [or ‘‘WO3 Æ H2O’’], 30 wt% aqueous H2O2 with R2Si(OR0 )2 in alkaline hydrogen peroxide–ethanol affords the dimeric title complexes. These compounds represent a type of silicon-based polyoxoperoxo species which are also obtained by grafting on silica surfaces and in the synthesis of organic/ inorganic mesophases to prepare MOx–SiO2– MCM-41 or MOx–SiO2–SBA-15.
2-
O
O O
O
M
O
O Si
R R
O O
O O
M O O
M = Mo or W R2 = (CH3)2, (i–Bu)2 or (CH3)(CH2Cl) Shen Lin, Ming-Xing Yang and Shi-Xiong Liu Polyhedron 26 (2007) 4793 Three novel trinuclear zinc(II)/nickel(II) complexes with pentadentate ligands N-nitrobenzoylsalicylhydrazidate
Dusˇanka D. Radanovic´, Urszula Rychlewska, Beata War_zajtis, Milica S. Cvijovic´, Mirjana Dj. Dimitrijevic´ and Milosˇ I. Djuran Polyhedron 26 (2007) 4799 Tuning the topologies of Co(II) and Ni(II) complexes with EDTA, 1,3-PDTA and 1,4BDTA ligands: Synthesis and spectroscopic data of [Mg(H2O)6][Co(1,4-bdta)] Æ 3H2O and [Mg(H2O)6][Ni(1,4-bdta)] Æ 3H2O complexes, and the X-ray structure of their chiral crystals
Elsevier Ltd.
Three novel trinuclear complexes Zn3(pnbzshz)2(C5H5N)4 (1), Ni3(p-nbzshz)2(py)4 (2) and Ni3(o-nbshz)2(DMF)2((CH3)2O)2 (3) have been obtained by the reaction of Zn(OAc)2 Æ 4H2O or Ni(OAc)2 Æ H2O with two new ligands, N-p-nitrobenzoylsalicylhydrazidate and N-o-nitrobenzoylsalicylhydrazidate. Complex 1 exhibits a one-dimensional wave-like chain structure resulting from the linkage of the phenolate oxygen donor atoms of the ligand between adjacent trinuclear zinc units. Complex 2 is an uncommon bent trinuclear nickel complex, whilst the three nickel atoms in complex 3 are arranged in a strictly linear fashion.
Stereochemically labile hexadentate cobalt(II) and nickel(II) complexes with 1,4-bdta ligand, [Mg(H2O)6][Co(1,4-bdta)] Æ 3H2O (a) and [Mg(H2O)6][Ni(1,4-bdta)] Æ 3H2O (b), have been synthesized and characterized by UV–Vis spectroscopy and X-ray crystallography. These complexes have been shown to undergo a spontaneous resolution upon crystallization, an unprecedented instance with this type of ligand.
iv
Rupa Shah, Vimal Soni, Aditya Prakash and Raj N. Mehrotra Polyhedron 26 (2007) 4809
Contents
Weak intermediate are involved in the oxidation of SO2 (aq) to SO42) by [ethylenebis(biguanide)]silver(II) in the acidic medium by successive one-electron transfer.
3+
H N
H2N
NH2 C
C
H2C
NH
N Ag
Kinetics and mechanism of oxidation of S(IV) by the ethylenebisbiguanide Ag(III) ion
H2C
N
C
Polyhedron 26 (2007) 4818 Dual-emissive complexes: Visible and nearinfrared luminescence from bis-pyrenyl lanthanide(III) complexes
Noemı´ Andrade-Lo´pez, Jose´ G. Alvarado-Rodrı´guez, Simplicio Gonza´lez-Montiel, Marı´a Guadalupe Rodrı´guez-Me´ndez, Marı´a Elena Pa´ez-Herna´ndez and Carlos Andre´s Gala´n-Vidal Polyhedron 26 (2007) 4825
The syntheses and photophysical attributes of a range of dual-emissive, bis-pyrenyl lanthanide complexes based on a DTPA architecture are described. Irradiation of the pyrene chromophore results in sensitised near-IR emission from NdIII, ErIII and YbIII.
The synthesis and characterization by X ray diffraction, NMR and mass spectrometry of complexes [Pd{(C5H4N)2Y}Cl2] (Y = CNMe, 5; Y = CH(OH), 6 and Y = CH(S2CNEt2), 7) is described. The ligands coordinate to the palladium atom in a bidentate mode. 5 displays a five-membered ring; 6 and 7 display six membered rings.
B. Machura, R. Penczek, R. Kruszynski, J. Kłak, J. Mrozin´ski and J. Kusz Polyhedron 26 (2007) 4833 A novel rhenium(III) complex with bis(pyrazol-1-yl)methane: X-ray structure and DFT calculations for [ReCl3(bpzm)(PPh3)] The [ReCl3(MeCN)(PPh3)2] complex reacts with bis(pyrazol-1-yl)methane (bpzm) to give [ReCl3(bpzm)(PPh3)]. The compound has been studied by IR, UV-Vis spectroscopy and X-ray crystallography. The molecular orbital diagram of [ReCl3(bpzm)(PPh3)] has been calcu-
NH2
NIR emission
O O
O
lated with the density functional theory (DFT) method. The spin-allowed triplet–triplet electronic transitions of [ReCl3(bpzm)(PPh3)] have been calculated with the time-dependent DFT method, and the UV–Vis spectrum of the title compound has been discussed on this basis. The magnetic behavior is characteristic of mononuclear complexes with d4 low-spin octahedral Re(III) complexes (3T1g ground state) and arise because of the large spin–orbit coupling (f = 2500 cm)1), which gives diamagnetic ground state.
N Ln
N O HN
390 nm O
N
337 nm
O O O
NH
Cl
H3C
Cl
Pd
N
N
N
G
N
N Pd
Cl 5
cis-Palladium(II) complexes of derivatives of di-(2-pyridyl)methane: Study of the influence of the bridge group in the coordination mode
Ag(H2L)+ + SO42- + 4H+
C N H
H2N
Simon J.A. Pope
+ SO2(aq)
NH
Cl
6 G= CH(OH) 7 G= CH(S2CNEt2)
Contents
Pradip Kumar Ghosh, Sushanta Saha and Ambikesh Mahapatra Polyhedron 26 (2007) 4841 Pd–Cl cleavage of dichloro-[1-alkyl-2-(naphthylazo)imidazole]palladium(II) complexes by picolinic acid: Kinetic and mechanistic studies
Qing-Feng Xu, Qiu-Xuan Zhou, Jian-Mei Lu, Xue-Wei Xia, Li-Hua Wang and Yong Zhang Polyhedron 26 (2007) 4849 Synthesis, structures and NLO properties of five non-centrosymmetric coordination compounds from the copper(II)/dps system (dps = 4,40 -dipyridyl sulfide)
R. Herna´ndez-Molina, I. Kalinina, P. Esparza, M. Sokolov, J. Gonzalez-Platas, A. Este´vez-Braun and E. Pe´rez-Sacau Polyhedron 26 (2007) 4860 Complexes of Co(II), Ni(II) and Cu(II) with lapachol
v
This work describes kinetics and mechanism of the reaction between picolinic acid (picH) and [Pd(a-/b-NaiR)Cl2] [a-/b-NaiR = 1-alkyl-2(naphthyl-a/b-azo)imidazole] in acetonitrile (MeCN) medium. The product is characterized as [Pd(a/b-NaiR)(pic)](ClO4) by different spectroscopic routes. It is established that the cleavage of Pd–Cl bond is the rate-determining step. Thermodynamic parameters (DH and DS) are determined from variable temperature kinetic studies.
A series of acentric coordination frameworks constructed by Cu(II) and 4,40 -dipyridyl sulfide (dps) were synthesized. All these coordination architectures are generated from achiral building blocks without any chiral auxiliary. The influence of anion and solvent on the structural architecture is discussed. Their second-order NLO properties are also studied.
The complexes of naturally occurring hydroxynaphtho-quinone, lapachol (HL) with Co(II), Ni(II) and Cu(II) have been prepared and the crystal structures of [CoL2(EtOH)2], [NiL2(EtOH)2] and [CuL2(py)2] reported. Characterisation by elemental analyses, cyclic voltammetry and FAB-MS was also performed.
O OH
O
Ann P. Hunter, Anthony M.J. Lees and Andrew W.G. Platt Polyhedron 26 (2007) 4865 Synthesis, structures and mass spectrometry of lanthanide nitrate complexes with tricyclohexylphosphine oxide
Complexes of lanthanide nitrates with tricyclolhexylphosphine oxide show variations in the nitrate coordination as the Ln3+ ionic radii decrease. Tandem mass spectra are simple showing loss of Cy3PO from the complex apart for the Yb complex which undergoes more extensive fragmentation.
O N L
O
O O
L
Er
O N L
O
O
La
N
L
L
O
O
Er
L L
O
O N O
L = Cy3PO
N
O
O O
N O
O O
L
O O
O
Tm
L
N
O
O
O
O
O
O N
O N
N
O
L O
O
O
O L
N O
L O
N
O
vi
Kiran A. Thabaj, Suresh D. Kulkarni, Shivamurti A. Chimatadar and Sharanappa T. Nandibewoor Polyhedron 26 (2007) 4877 Oxidative transformation of ciprofloxacin by alkaline permanganate – A kinetic and mechanistic study
Mei-Lin Ho, Yi-Ming Cheng, Lai-Chin Wu, Pi-Tai Chou, Gene-Hsiang Lee, Fang-Chi Hsu and Yun Chi
Contents
The general scheme is proposed for oxidative transformation of ciprofloxacin, an antibacterial agent by alkaline permanganate to explore the observed experimental results. Products and intermediates were identified by LC-ESIMS/MS technique. Derived rate law consistent with the observed kinetics is Rate ¼
MnO4- + OH[MnO4 OH]
2-
+ Ar N
NH
Complex C
K1 K2 k slow
[MnO4 OH]
2-
Complex (C) +.
Ar N
2-
NH + MnO4
+ OH-
Followed by other fast steps to give products.
kK 1 K 2 ½MnO 4 ½OH ½CF : 1 þ K 1 ½OH þ K 1 K 2 ½OH ½CF
The emission of 1 (2 · 10)5 M in acetonitrile, left) and 1 in the presence of 4 · 10)6 M solution of Pb2+ excited at 365 nm (UV lamp).
Polyhedron 26 (2007) 4886 Probing Pb2+ cation via the iridium based phosphorescent dye
Ilia Sokka, Andreas Fischer and Lars Kloo Polyhedron 26 (2007) 4893 Optimization of the synthesis of non-symmetrical alkyl dimethyl sulfonium halides
Sergey N. Semenov, Andrey Yu. Rogachev, Svetlana V. Eliseeva, Yury A. Belousov, Andrey A. Drozdov and Sergey I. Troyanov Polyhedron 26 (2007) 4899 5-Nitroaminotetrazole as a building block for extended network structures: Syntheses and crystal structures of a number of heavy metal derivatives
A high-yield, one-step synthesis of sulfonium halogenides with long alkyl chains is described. A polar electrophilic solvent, trifluoroacetic acid, was used as reaction medium. Dodecyl dimethyl sulfonium, hexadecyl dimethyl sulfonium bromides and chlorides of high purity were obtained and characterized. The crystal structure of hexadecyl dimethyl sulfonium bromide has been determined.
Two extended network structures with the formulas [Pb(CHN6O2)2(H2O)4]n and [Hg(CN6O2)(H2O)2]n were obtained from 5nitroaminotetrazole, both complexes were characterized by X-ray crystallography. The influence of chemical hardness and charge distribution on the reactivity and coordination properties of 5-nitroaminotetrazole have been estimated based on density functional calculations.
Alk-X + S
CF3COOH
Alk
Alk = n-CH3(CH2)10CH2-, n-CH3(CH2)14CH2X = Cl, Br
S
X-
Contents
Vahid Amani, Nasser Safari, Hamid Reza Khavasi and Peiman Mirzaei Polyhedron 26 (2007) 4908 Iron(III) mixed-ligand complexes: Synthesis, characterization and crystal structure determination of iron(III) hetero-ligand complexes containing 1,10-phenanthroline, 2,20 -bipyridine, chloride and dimethyl sulfoxide, [Fe(phen)Cl3(DMSO)] and [Fe(bipy)Cl3(DMSO)]
Hsi-Ying Hsieh, Ching-Wen Cheng, Fuh-An Yang, Jyh-Horung Chen, Jo-Yu Tung, Shin-Shin Wang and Lian-Pin Hwang Polyhedron 26 (2007) 4915 The structures of (phenylato)(N-2-thiophenecarboxamido-meso-tetraphenylporphyrinato)mercury(II) and bisphenylmercury(II) complex of 21-(4-tert-butyl-benzenesulfonamido)5,10,15,20-tetraphenylporphyrin
Subal Chandra Manna, Joan Ribas, Ennio Zangrando and Nirmalendu Ray Chaudhuri Polyhedron 26 (2007) 4923 Dipyridyl bridged coordination polymers of Cu(II): Synthesis, crystal structure and magnetic study
Elena Ioachim, Elaine A. Medlycott, W.G. Skene and Garry S. Hanan Polyhedron 26 (2007) 4929 Synthesis and properties of 6,60 -dithienyl-4,40 bipyrimidine and its hetero- and homo-leptic Ru(II) complexes
[Fe(bipy)Cl3(DMSO)] and [Fe(phen)Cl3(DMSO)] complexes (where bipy is 2,20 -bipyridine, phen is 1,10-phenanthroline and DMSO is dimethyl sulfoxide) were prepared and characterized by elemental analysis, IR, UV–Vis and 1H NMR spectroscopies and by the X-ray diffraction method.
We have investigated two new diamagnetic porphyrin complexes, namely, mononuclear mercury(II) complex of 6 Æ CH2Cl2 Æ 0.5C6H14 and dinuclear mercury(II) complex of 7, and their X-ray structures are established.These two porphyrins complexes are of SAT type. The tetracoordination for the Hg(1) in 6 Æ CH2Cl2 Æ 0.5C6H14 and Hg(2) in 7 is demonstrated and a linear coordination is described for the Hg(1) in 7.
Coordination polymers, [Cu(bpp)(H2O)2(ClO4)2]n (1) and {[Cu(bpds)2(ClO4)2] Æ 1.5(H2O)}n (2) [bpp, 1,3-bis(4-pyridyl)propane and bpds, 4,40 -bipyridyl disulfide] have been synthesized and characterized by X-ray single crystal diffraction study and magnetic measurement.
A new bis(thienyl)-bipyrimidine ligand readily forms Ru(II) complexes which emit at significantly lower energy than the parent Ru(bpy)32+ complex.
vii
[Fe(N-N)Cl4][N-N.H]
CH3OH/DMSO
N-N is bipyridine and phenanthroline
[Fe(N-N)Cl3(DMSO)] + N-N. HCl
viii
Marco Bortoluzzi, Emilio Bordignon, Gino Paolucci and Bruno Pitteri Polyhedron 26 (2007) 4936 A computational study on mixed-ligand N2P3 donor-set iron(II) and ruthenium(II) classical and non-classical hydrides
Andrei S. Zelenev, Josepha M. Fu and Bruce A. Keiser Polyhedron 26 (2007) 4941 Establishing the difference between colloidal borosilicate and boron-modified colloidal silica via chelation of boron with catechol and D L -tartaric acid
Teresa F. Mastropietro, Donatella Armentano, Nadia Marino and Giovanni De Munno Polyhedron 26 (2007) 4945 Metal–nucleobase interactions in magnesium(II) and manganese(II) complexes with adenine: Influence of the anion on the noncovalent stabilization of 7H-adenine tautomer
Matthew C. Hales and Ray L. Frost Polyhedron 26 (2007) 4955 Synthesis and vibrational spectroscopic characterisation of synthetic hydrozincite and smithsonite
Contents
The results of DFT calculations on hydride complexes of the type [MH(N–N)P3]+ and [M(g2-H2)(N–N)P3]2+ {M = Fe, Ru; N–N = 2,20 -bipyridine (bpy), 1,10-phenanthroline (phen); P = PH3, PF3}, are described. A good correlation between various computed molecular properties and experimental data reported in the literature is highlighted. The charge distributions obtained from DFT calculations allow to hypothesize that the different acidities of iron and ruthenium nonclassical hydrides could be mainly justified on the basis of the difference of electronegativity of the two metal ions considered.
Colloidal borosilicate and boron-modified colloidal silica sols both contain B–O–Si chemical bonds that can be detected by 11B NMR. While the boron present in colloidal borosilicate is stable towards the action of catechol and tartaric acid, the boron in boronmodified silica is readily complexed by these agents.
The synthesis and crystal structure of the compounds [Mg(H2O)6X2 Æ 2ade] (with X = Cl) (1), Br) (2), ClO4) (3)), [Mn(H2O)4 Æ (ade)2 Æ (ClO4)2] (4), and [Mn2(H2O)6 Æ (ade)2 Æ (NO3)4 Æ 2H2O] (5) (where ade = adenine) are reported. Compounds 1–3 consist of self-assembled hexaaquo Mg(II) ions, ade molecules and anions. Compounds 4 and 5 represent a rare example of direct Mn–N binding involving isolated nucleobases and the first one containing ade as ligand. The detailed analysis of non-covalent interactions in all the compounds prove that the anions play a crucial role in determining the non-covalent stabilization of the minor 7Hadenine tautomer.
Hydrozincite and smithsonite were synthesised by controlling the partial pressure of CO2 resulting from the reaction in solution of zinc chloride and sodium bicarbonate. Raman spectroscopy complimented with infrared spectroscopy has been used to characterise the vibrational spectra of these synthesised minerals.
Contents
Hamid Khanmohammadi, Razyeh Arabahmadi, Mohammad H. Abnosi and Hamid R. Khavasi Polyhedron 26 (2007) 4963 Synthesis, crystal structure, spectral and biological studies of CuII–MII(M = Zn and Pb) heterodinuclear complexes of new phenolbased macrocyclic ligands
Subrata Patra, Eringathodi Suresh and Parimal Paul Polyhedron 26 (2007) 4971 Functionalized calix[4]arene as an ionophore: Synthesis, crystal structures and complexation study with Na+ and K+ ions
ix
A series of heterodinuclear Cu(II)–M(II) (M = Pb and Zn) complexes of new phenolbased compartmental macrocyclic ligands, possessing contiguous (N2O2) and (NxO2) (x = 2, 3) coordination sites, was prepared and their biological activity has been tested in vitro. The crystal structure of [CuZn L3(H2O)](ClO4)2 was determined by X-ray diffraction and shows that the Zn(II) and Cu(II) centres reside in the N2O2 sites of the macrocyclic ligand.
A family of trisubstituted calix[4]arenes with a partial cone conformation has been synthesized and structurally characterized. Crystal structural analyses show that the precise shape of the molecule, and intra- and intermolecular interactions (C–H p, p p and C–H O) of these compounds are significantly different due to the variation of the substituents. A complexation study with Na+ and K+ ions reveal that one of the ionophores (L3) selectively forms a complex with the latter ion.
OR
O
OR
OH
OH2 Cl
K+
O
Cl
O
OH2 O
OH OR
OR
R = -C H 2C H 2C H 3
Li-Ying Wang, Quan-Ling Suo, Li-Min Han, Yi-Bing Wang and Lin-Hong Weng Polyhedron 26 (2007) 4981 Synthesis and structural characterization of new p-ferrocenylphenylacetylene bridged cobalt carbonyl clusters
Zheng-Xing Zhang, Yan-Rong Li, Rui-Ting Liu, Zhen-Xia Chen, Lin-Hong Weng and Xi-Geng Zhou Polyhedron 26 (2007) 4986 Insertion reaction of elemental sulfur into the Ln–C bond: Synthesis and characterization of [(C5H4SiMe2tBu)2Ln(l-SR)]2 (R = Me, Ln = Yb, Er, Dy, Y; R = nBu, Ln = Yb, Dy)
A new ferrocenylphenyl butadiynyl compound L and three new complexes 1, 2 and 3 have been synthesized. The composition and structure of the four compounds were characterized by elemental analysis, FTIR, NMR and MS. The molecular and crystal structures of L and 2 were analyzed by X-ray single crystal diffraction.
Treatment of (C5H4SiMe2tBu)2LnR with elemental sulfur leads to the formation of dimeric complexes [(C5H4SiMe2tBu)2Ln(l-SR)]2 [R = Me, Ln = Yb, Er, Dy, Y; R = nBu, Ln = Yb, Dy], providing a new route to the syntheses of lanthanocene thiolates.
(C 5H 4SiMe 2tBu)2 LnR
1/8 S8 toluene, rt
[(C5 H4 SiMe2 tBu)2 Ln(μ − SR)]2
R = Me, Ln = Yb, Er, Dy, Y; R = nBu, Ln = Yb, Dy
x
Tarlok S. Lobana, Gagandeep Bawa, Geeta Hundal, A.P.S. Pannu, Ray J. Butcher, Ben-Jie Liaw and Chen W. Liu Polyhedron 26 (2007) 4993 The influence of substituents (R) at the C2 carbon on bonding properties of thiosemicarbazones {RC2(H)@N3-N2H–C1(@S)–N1H2} in palladium(II) complexes Reactions of the PdCl2(PPh3)2 precursor with furan-2-carbaldehyde thiosemicarbazone (Hftsc) and thiophene-2-carbaldehyde thiosemicarbazone (Httsc), in 1:1 molar ratios in the presence of Et3N base, removed one Cl and
Ricardo C. Santana, Jesiel F. Carvalho, Ivo Vencato, Hamilton B. Napolitano, Adailton J. Bortoluzzi, Gasto´n E. Barberis, Raul E. Rapp, Mario C.G. Passeggi and Rafael Calvo Polyhedron 26 (2007) 5001 Synthesis, crystal structure and magnetic properties of a new dinuclear copper(II) amino acid complex [Cu2(L -arg)2(l-HPO4-O)(l-HPO4O,O0 )(l-OH)]) Æ (H3O)+ Æ (H2O)6
Joaquı´n Borra´s, Gloria Alzuet, ´ lvarez, Francisco Estevan, Marta Gonza´lez-A Benigno Macı´as, Malva Liu-Gonza´lez and Alfonso Castin˜eiras Polyhedron 26 (2007) 5009 Crystal structures and spectroscopic properties of copper(II)–bis(2-pyridylcarbonyl)amide– chlorobenzoate complexes
P.N. Remya, C.H. Suresh and M.L.P. Reddy Polyhedron 26 (2007) 5016 Rapid reduction and complexation of vanadium by 1-phenyl-3-methyl-4-toluoyl-5-pyrazolone: Spectroscopic characterization and structure modelling
Contents
one PPh3 group from the PdII center, and yielded the complexes, [Pd(g2-N3,S-ftsc)(PPh3)Cl] (1) and [Pd(g2-N3,S-ttsc)(PPh3)Cl] (2), respectively, However, when a 1:2 molar ratio (M:L) was used, both the Cl and PPh3 ligands were removed, yielding complexes, [Pd(g2-N3,S-ftsc)2] (3) and [Pd(g2-N3,S-ttsc)2] (4). In contrast, reactions with pyrrole-2-carbaldehyde thiosemicarbazone, (H2ptsc) and salicylaldehyde thiosemicarbazone, (H2stsc) in 1:1 or 1:2 molar ratios have invariably formed the complexes [Pd(g3-N4,N3,S-ptsc)(PPh3)] (5) and [Pd(g3–O,N3,S-stsc)(PPh3)] (6), respectively.
The synthesis, characterization and crystal structure of a novel dinuclear copper compound with L -arginine, mono and bidentate HPO42) oxoanions and an OH) anion are reported. The dinuclear character and bridging scheme, rare for metal–amino acid compounds, is attributed to the bonding characteristic of the phosphate anions. The magnetic properties and EPR spectra indicate an antiferromagnetic intradinuclear interaction J/kB = )3.7 K and a ferromagnetic coupling between these dinuclear units of J0 /kB 0.3 K.
The reaction of 2,4,6-tris(pyridyl)-1,3,5-triazine (ptz) and copper(II) salts in DMF–water resulted in the hydrolysis of ptz, giving rise to the bis(2-pyridylcarbonyl)amide anion (ptO2)) and affording the complexes [Cu(ptO2)(2Clbenz)(H2O)], [Cu(ptO2)(3-Clbenz)], and [Cu(ptO2)(4-Clbenz)(DMF)]. This report includes the chemical, the spectroscopic characterization and the crystal structures of all these compounds.
The reduction of vanadium(V) by 1-phenyl-3methyl-4-toluoyl-5-pyrazolone over the pH range of 1.0–7.0 has been assessed by various spectroscopic techniques. The reaction proceeds by the transfer of one electron to vanadium(V) by the ligand via the formation of a free-radical intermediate, and subsequently the reduced vanadium species rapidly complexes with the available free ligand and forms vanadyl complex. These reduction reactions occur under physiological conditions and thus could be important to the reduction of vanadium(V)-containing coordination compounds used as insulin-enhancing agents for treatment of diabetics.
Contents
Habibar Chowdhury, Rajarshi Ghosh, Sk. Hafijur Rahaman and Barindra Kumar Ghosh Polyhedron 26 (2007) 5023 Syntheses, X-ray structures and properties of a dinuclear cadmium(II)azido and a polymeric cadmium(II)thiocyanato compounds containing bis(tridentate) congregators One-pot reactions of cadmium(II) perchlorate/ nitrate, Schiff bases (pbap/pfap) and pseudohalides (sodium azide/ammonium thiocyanate) in a 2:1:4 molar ratio in MeOH–MeCN solvent mixtures at room temperature result in a di-
Alina Bien´ko, Julia Kłak, Jerzy Mrozin´ski, Sławomir Domagała, Bohdan Korybut-Daszkiewicz and Krzysztof Woz´niak Polyhedron 26 (2007) 5030 Magnetism and crystal structures of CuIIMnII and CuIINiII ordered bimetallic chains The syntheses, crystal structures and magnetic properties of the new bimetallic compounds {CuLa[Ni(NCS)4(H2O)2]} (1) and {CuLa[Mn(NCS)4(H2O)2]} (2), where L = N-dl-5,12-dimethyl-1,4,8,11tetraazacyclotetradeca-4,11-diene, are reported. Both structures consist of well-separated and magnetically equivalent layers which are composed of thiocyanate-
Padavattan Govindaswamy, Yurij A. Mozharivskyj and Mohan Rao Kollipara Polyhedron 26 (2007) 5039 New pentamethylcyclopentadienyl rhodium and iridium complexes containing arylazoimidazole ligands: Crystal and molecular structure of the complex [(g5-C5Me5)RhCl(Me– C6H4–N@N–C3H3N2)]+
Tamara V. Basova, Ays¸e G. Gu¨rek, Devrim Atilla, Aseel K. Hassan and Vefa Ahsen Polyhedron 26 (2007) 5045 Synthesis and characterization of new mesomorphic octakis(alkylthio)-substituted lead phthalocyanines and their films
nuclear compound [Cd2(pbap)(OH2)2(N3)4] (1) [pbap = N-(1-pyridin-2-ylbenzylidene)-N-[2(4-{2-[(1-pyridin-2-ylbenzylidene)amino]ethyl}piperazin-1-yl)ethyl]amine] and a polymeric compound [Cd2(pfap)(l1,3-NCS)(l1,3SCN) (NCS)2]n (2) [pfap = N-(1-pyridin-2ylformylidene)-N-[2-(4-{2-[(1-pyridin-2ylformylidene) amino]ethyl}piperazin-1-yl)ethyl]amine]. X-ray crystal structural analyses reveal a bis (tridentate) congregation behaviour of the hexadentate blocker (pbap/pfap) encapsulating two metal centers. Both the complexes display intraligand 1(p–p*) fluorescence and intraligand 3(p–p*) phosphorescence in glassy solutions.
bridged Cu(II)–Mn(II) or Cu(II)–Ni(II) binuclear units and create infinite polymeric zig-zag-like chains in the crystal lattices. The [Ni(NCS)4(H2O)2] and [Mn(NCS)4(H2O)2] molecular fragments have a distorted octahedral symmetry. The geometry of the Cu(II) unit is octahedral with the apical positions occupied by bridging thiocyanate ligands and the basal ones by four nitrogen atoms from the macrocyclic ring. The shortest intramolecular M–M dis˚ (Cu–Ni) and 6.421 A ˚ (Cu–Mn). tances are: 6.342 A Magnetic susceptibility and magnetization measurements for the examined compounds have been carried out over the range 1.8–300 K. The data suggest antiferromagnetic interactions through the thiocyanate bridge. Finally, the magnitudes of the Cu(II)– M(II) interactions (M = Ni and Mn) have been compared and qualitatively rationalised.
The dimeric complexes [{(g5-C5Me5)M(lCl)Cl}2] where M = Rh and Ir reacts with several arylazoimidazole (RaaiR0 ) ligands to give the mononuclear cationic complexes of the type [(g5-C5Me5)MCl(RaaiR0 )]+. The molecular structure of the complex [(g5-C5Me5)RhCl(Me–C6H4–N@N–C3H3N2)]+ 4[PF6] was established by single crystal X-ray diffraction study.
The syntheses of new octakis (alkylthio)-substituted phthalocyanines of Pb(II) (1a and 2a) are described. These phthalocyanine derivatives are liquid at room temperature and form columnar-hexagonal (Colh) mesophases below )10 C. Thin films of octakis(alkylthio)-substituted Pb(II) phthalocyanines 1a and 2a were prepared by the method of spin-coating.
xi
xii
Qing Su, Qiao-Lin Wu, Guang-Hua Li, Xiao-Ming Liu and Ying Mu Polyhedron 26 (2007) 5053 Bis-salicylaldiminato zinc complexes: Syntheses, characterization and luminescent properties Bis-salicylaldiminato zinc complexes with four new salicylaldiminato ligands: (Ar1 = 7-(2,4-Me2) (Ar1N=HCAr2O)2Zn C9H4N, Ar2 = C6H4 (2a); Ar1 = 7-(2,4-Me2)
Susobhan Biswas, Saikat Sarkar, Ian M. Steele, Sougata Sarkar, Golam Mostafa, Bijali Bikash Bhaumik and Kamalendu Dey Polyhedron 26 (2007) 5061 Two-dimensional supramolecular assembly of phenylmercury(II) and cadmium(II) complexes with a tridentate thiohydrazone NNS donor ligand: Synthesis, coordination behavior and crystal structure
Raif Kurtaran, Sinem Odabas¸ıog˘lu, Akin Azizoglu, Hu¨lya Kara and Orhan Atakol Polyhedron 26 (2007) 5069 Experimental and computational study on [2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine] (dithiocyanato)mercury(II) The mercury complex of 2,6-bis(3,5-dimethylN-pyrazolyl)pyridine (bdmpp) has been synthesized and characterized by X-ray diffraction, IR, UV–Vis and TGA–DTA methods. The structure consists of units in which the
Jeanet Conradie, Gert J. Lamprecht, Andreas Roodt and Jannie C. Swarts Polyhedron 26 (2007) 5075 Kinetic study of the oxidative addition reaction between methyl iodide and [Rh(FcCOCHCOCF3)(CO)(PPh3)]: Structure of [Rh(FcCOCHCOCF3)(CO)(PPh3)(CH3)(I)]
Contents
C9H4N, Ar2 = 3,5-tBu2C6H2 (2b); Ar1 = 7(2,4-Me2)C9H4N, Ar2 = 5-BrC6H3 (2c); Ar1 = 7-(2,4-Me2)C9H4N, Ar2 = 3,5-Br2C6H2 (2d)) have been synthesized and characterized by elemental analyses, 1H, 13C NMR and IR spectroscopy.The molecular structure of complex 2b was confirmed by X-ray crystallography, showing intermolecular p–p interactions in the solid state.These complexes produce bright fluorescence in both solution and the solid state. In addition, the emission color in solution can be tuned in the range 503–532 nm by the modification of the salicylaldiminato ligand.
The reaction of diacetylmonoxime and morpholine N-thiohydrazide with phenylmercury(II) acetate and cadmium(II) acetate formed the novel phenylmercury(II) complex, [PhHg(Hdammthiol)] (1) and the cadmium(II) complex, [Cd(Hdammthiol)2] (2), respectively (where H2dammthiol is the thiol form of diacetylmonoximemorpholine N-thiohydrazone (Hdammth)). Both complexes form two-dimensional supramolecular sheet and a new non-conventional CH3 O interaction (in cadmium complex).
mercury atom is a penta-coordinated by two sulfur and three nitrogen atoms. [Hg(bdmpp)(SCN)2] has a distorted square pyramidal geometry. The optimized geometry at both PM3 and DFT methods agrees with the X-ray structure well. The infrared spectra of the title complex was studied in the 4000– 400 cm)1 frequency range experimentally and theoretically. The experimental results are in better agreement with the DFT results at the B3LYP/LanL2DZ level than the semi-empirical results at the PM3 level.
The chemical kinetics, studied by UV/Vis, IR, H and 31P NMR techniques, of oxidative addition of CH3I to [Rh(FcCOCHCOCF3)(CO)(PPh3)] with Fc = ferrocenyl, consist of three definite sets of reactions and involves geometrical isomers of two different RhIIIalkyl and two different RhIII-acyl species. 1
F3C
F3C Rh O
CO
PPh3 CO Rh O CH3 O
PPh3
O
CH 3 I
I
Fe
Fe
Kc F3C
H3C CO
O
Rh
PPh3
Fe
Rh(I) isomers
PPh3
O
Rh O
O
C
F3C O
I
Fe
+ other geometrical isomers
Contents
P.F. Rapheal, E. Manoj and M.R. Prathapachandra Kurup Polyhedron 26 (2007) 5088 Syntheses and EPR spectral studies of manganese(II) complexes derived from pyridine-2carbaldehyde based N(4)-substituted thiosemicarbazones: Crystal structure of one complex Five manganese(II) complexes {½MnL1 2 H2 O EtOH, [Mn(L1)(HL1)]OAc, ½MnL1 2 3H2 O, ½MnL1 2 3H2 O and [Mn(HL3)2](SCN)2 Æ MeOH} of three NNS donor N(4)-
Timothy J. Boyle, Harry D. Pratt III, Todd M. Alam, Mark A. Rodriguez and Paul G. Clem Polyhedron 26 (2007) 5095 Synthesis and characterization of solvated trifluoroacetate alkaline earth derivatives
Subhra Basak, Soma Sen, Sambuddha Banerjee, Samiran Mitra, Georgina Rosair and M.T. Garland Rodriguez Polyhedron 26 (2007) 5104 Three new pseudohalide bridged dinuclear Zn(II) Schiff base complexes: Synthesis, crystal structures and fluorescence studies
Kjell Ove Kongshaug and Helmer Fjellva˚g Polyhedron 26 (2007) 5113 Syntheses, structures and magnetic properties of Mn(II) containing 3D polymeric networks
substituted thiosemicarbazone ligands {pyridine-2-carbaldehyde N(4)-p-methoxyphenyl thiosemicarbazone [HL1], pyridine-2carbaldehyde N(4)-2-phenethylthiosemicarbazone [HL2] and pyridine-2-carbaldehyde N(4)-methyl, N(4)-phenyl thiosemicarbazone [HL3]} were synthesized and physico-chemically characterized. The crystal structure of the compound ½MnL1 2 H2 O has been determined by X-ray diffraction studies. It is found to have a distorted octahedral geometry. EPR spectra in DMF solutions at 77 K show hyperfine sextets with low intensity forbidden lines lying between each of the two main hyperfine lines.
A series of alkaline earth trifluoracetic acid (TFA) derivatives were crystallographically characterized as: Mg(TFA)2(py)4 (1), {[Ca2(lTFA)3(THF)4](l-TFA)}n (2), {[(l-TFA)2Sr(lc-TFA)][H-py]py}n(3); and {[Ba(lc-TFA)2(lc-TFA)(py)][H-py]}n (4) (shown). Elemental analyses, solid-state, and solution multinuclear NMR, and FTIR data confirms the bulk powders were consistent with the X-ray structures.
Three new dinuclear Zn(II) complexes [Zn(L)(l1,1-N3)Zn(L)(N3)] Æ 1.5H2O (1), [Zn(L)(l1,1-NCO)Zn(L)(NCO)] Æ 1.5H2O (2) and [Zn(L)(l1,1-NCS)Zn(L)(NCS)(OH2)] (3) of the Schiff base ligand LH [LH = (OCH3)(OH)C6H3CHN(CH2)2N(CH3)2] have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, TGA, fluorescence and single crystal X-ray diffraction studies. All the synthesized complexes display intraligand 1(p–p*) fluorescence and can serve as potential photoactive materials.
Two novel coordination polymers based on Mn(II) have been prepared, and their crystal structures have been solved by single crystal Xray diffraction. Thermal and magnetic properties are discussed.
xiii
xiv
J.G. Małecki, R. Kruszyn´ski, D. Tabak and J. Kusz Polyhedron 26 (2007) 5120 The reactions between [RuHCl(CO)(PPh3)3] and quinoline carboxylic acids The reactions of [RuHCl(CO)(PPh3)3] with 8hydroxy-2-methyl-quinoline-7-carboxylic acid and quinoline-2-carboxylic acid have been examined, and two novel ruthenium(II) complexes – [(PPh3)2RuH(CO)(C10H8NO3)] and [(PPh3)2RuCl(CO)(C9H6O2)] – have been obtained. The compounds have been studied by
Ramesh Kapoor, Ashok Kataria, Pratibha Kapoor, Ajay Pal Singh Pannu, Maninder Singh Hundal and Montserrat Corbella Polyhedron 26 (2007) 5131 Synthesis, X-ray structure and magnetic studies of Cu(II) complexes of tridentate SNS ligands (S-dbpt, N,N,N0 ,N0 -tetraisobutylpyridine-2,6-dithiocarboxamide; S-dppt, N,N, N0 ,N0 -tetraisopropylpyridine-2,6-dithiocarboxamide): Role of steric factors on the geometry around Cu(II)
Joy Chakraborty, Santarupa Thakurta, Brajagopal Samanta, Aurkie Ray, G. Pilet, Stuart R. Batten, Paul Jensen and Samiran Mitra Polyhedron 26 (2007) 5139 Synthesis, characterisation and crystal structures of three trinuclear cadmium(II) complexes with multidentate Schiff base ligands Three novel trimeric Cd(II) complexes have been prepared from two different symmetrical Schiff bases. Crystal structures of all the complexes have been established by single crystal
Marisa Belicchi-Ferrari, Franco Bisceglie, Giorgio Pelosi, Silvana Pinelli and Pieralberto Tarasconi Polyhedron 26 (2007) 5150 Synthesis, characterization, crystal structure and antiproliferative in vitro activity of longchain aliphatic thiosemicarbazones and their Ni(II) complexes
Contents
IR and UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagrams of the complexes have been calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of the compounds have been calculated with the time-dependent DFT method, and the UV–Vis spectra of the compounds have been discussed on this basis.
HOOC
N
Cl
CH3
O Ph3P
N
Ru
Ru
PPh3 C
H
CO
CO
PPh3 PPh3
O
O
Two new tetranuclear copper(II) complexes, each formed by a cationic and an anionic dinuclear species are reported. Both of them, characterized by X-ray diffraction, show the same anionic complex [{CuCl2}2(l-Cl)2]2) which shows weak antiferromagnetic coupling. The dinuclear cationic species [{Cu(S-dbpt)}2(l-Cl)2]2+ shows ferromagnetic behaviour.
X-ray diffraction methods. The ligands and their metal complexes have been characterised by analytical and spectroscopic techniques. Among the three complexes, 1 and 3 are linear whereas 2 is a cyclic trimer. In 1 and 3, all the doubly phenoxo bridged Cd(II) metal centres have a distorted octahedral environment. In the complex 2, two out of the three Cd(II) centres reside in a distorted octahedral environment and the remaining one enjoys a monocapped octahedral geometry. Altogether a variety in the bridging mode of two new salen-type ligands has been established.
Nine long-chain aliphatic thiosemicarbazones and their nickel complexes were prepared and characterized by spectroscopic methods and for five of the complexes also by X-ray crystallography diffraction analysis. Heptanal thiosemicarbazone and the corresponding nickel complex were chosen after a solubility/ stability test to carry out preliminary experiments in vitro on human leukemia cell line U937. The complex possesses a remarkable biological activity in inhibiting cell growth and in inducing apoptosis.
N1 N2 S1
C3
C1 N3
C4 C2
Ni1
C6
C5 C7
C8
Contents
ˇ eljka Soldin, Gordana Pavlovic´, Z Zora Popovic´ and Vesna Tralic´-Kulenovic´ Polyhedron 26 (2007) 5162 Synthesis and characterization of mercury(II) complexes with 2-styryl-1,3-benzothiazole (sb). Presence of two differently coordinated Hg(II) ions in the dinuclear complex Hg2Cl4(sb)3. Structural characterization of 2-styryl-1,3-benzothiazole and some of its derivatives
Hui Wang, Ming-Xing Li, Min Shao and Xiang He Polyhedron 26 (2007) 5171 Syntheses, structures and luminescent properties of four copper(I) cyanide coordination polymers based on 2-(n-pyridyl)benzimidazole ligands (n = 2,3,4)
Kou-Lin Zhang, Hong-Yan Gao, Zi-Cai Pan, Wei Liang and Guo-Wang Diao Polyhedron 26 (2007) 5177 Preparation and characterization of two threedimensional metal–organic photoluminescent supramolecular networks Two novel photoluminescent coordination compounds of the formula [Cd(atpt)phen(H2O)] Æ H2O (1) and [Zn2(atpt)2(bipy)2(H2O)2] (2) (H2atpt = 2aminoterephthalic acid, bipy = 2,20 -bipyridine and phen = 1,10-phenanthroline) were synthesized through the self-assembly of H2atpt and N-containing ligands (bipy for 1 and phen for 2) with metal(II)
Laure Latapie, Julien Le Gal, Bassem Hamaoui, Joe¨l Jaud, Marie Gressier and Eric Benoist Polyhedron 26 (2007) 5185 First examples of neutral rhenium(V) complexes with a novel semi-rigid ligand containing a P,N,N,S donor atom set: Synthesis, characterisation and crystal structure
Mercury(II) chloride and bromide form two novel complexes 2 and 5 with 2-styryl-1,3benzothiazole (sb). Compounds with different nuclearities were obtained under identical reaction conditions (ethanol medium, 1:2 molar ratio). The structure of 2 consists of dinuclear Hg2Cl4(sb)3 units and compound 5 of monomeric HgBr2(sb)2 units.
Four copper(I) cyanide coordination polymers containing 2-(n-pyridyl)benzimidazole ligands were synthesized. They possess one-dimensional linear chain, ladder-like double chain, saddle-shaped helical chain, and two-dimensional layer polymeric structures.
ions in the presence of NaOH, and characterized by FT-IR spectroscopy, thermogravimetric analysis (TG), X-ray analysis and photoluminescence spectra in the solid state. The coordination mode of the atpt ligand in 2 is novel and is first reported in this presentation. Compound 1 shows a 1D architecture and further assembles into a 3D supramolecular network via interchain hydrogen bonds and p–p stacking interactions. Compound 2 exhibits a binuclear structure with intramolecular p–p stacking interactions, which is further extended into a 3D supramolecular framework via intermolecular hydrogen bonds and C–H p interactions. Compounds 1 and 2 exhibit green photoluminescence in the solid state at room temperature.
The synthesis of a novel PN2S-tetradentate ligand [Ph-P(Ph2)N2S(Trt)] (2) and its metal complexation with ReV precursors have been studied. Whilst the reaction of 2 with ReOCl3(PPh3)2 gave the expected stable complex [ReO{Ph-P(Ph2)N2S}] (4), an unexpected neutral and diamagnetic species, [ReN{PhP(Ph2)N2S(Trt)}] (5), has been isolated during the complexation of 2 with ReNCl2(PPh3)2.
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Corrigendum to ‘‘Structural diversities and spectroscopic properties of bis and tris (1,10-phenanthroline)copper(II) complexes’’ [Polyhedron 26 (2007) 1459–1468] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5191
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