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12. Platinum 1993
Coordination Chemistry Reviews 146 (1995)
ELSEVIER
431-450
12.
Platinum
Peter
1993
K. Byers
CONTENTS INTRODUCTION . .... . .. .... .. ... .. .. .. .. .. . .... .. .. ... .. .. .... .. . ..__......... .... .. .. .._...... .. . .. .. .. .... . .. .... 12.1 PLATINUM(IV) .. .._...... .... .. .. .... .. ... .... .. .. .... .. .. ... .. .. .... .. .. .. .. .. ..... .. .... .. .. .... . .... .. .. 12.2 PLATINUM(I1) .... .. .. .. .. .. .. .... . ... .... .. .. .... . . .... .. .. .... .. .. .... .. .... .. .. ... . .. .... .. .. .. .. .. .... .. 12.2.1 domplexes with phosphine donor ligands ................................ 12.2.2 Complexes with nitrogen donor ligands .................................... 12.2.3 Complexes with sulfur group donor ligands ............................. 12.2.4 Complexes with mixed donor ligands ....................................... 12.3 PLATINUM(I) ................................................................................................ 12.4 PLATINUM(O) ............................................................................................... REFERENCES ..........................................................................................................
431 431 432 432 441 443 444 z:: 448
INTRODUCTION The coordination
chemistry of platinum reported during the year 1993 has been reviewed.
Although this account does not intend or claim to be comprehensive,
examples have been selected to
represent important features. Only the primary journals are covered and were searched using both platinum (and related) as a keyword and being present in the title. The review covers the chemistry of platinum in its 0 + +4 oxidation states, but does not include the catalytic activity of platinum complexes, nucleoside
complexes
bases. Classification
atom. For complexes donors
containing
have priority
only Pt-C bonds or complexes
of the complexes
is according
containing
to the oxidation
nucleotide
or
state and donor
containing mixed donor sets the priority ordering P>N>S applies, and neutral over charged
donor atoms; mixed
donor didentate
ligands
are treated
separately. PLATINUM(IV)
12.1
Reaction
of [PtMez(phen)]
[Pt(Me)z(ER)z(phen)]
SMe, SPh, SePh) gives
(1) as a mixture of truns- (major) and cis- (minor) isomers. For (1; ER =
SePh) the solid state structure platinum(IV)
with RE-ER (ER = OH, OC(O)Ph,
was determined
iodide [PtMej(p-I)]4
by X-ray crystallography
with the aminothiol HS(CH2)2NEt2
trinuclear species [(PtMeg)s( (p-I), p-S(CH2)2NHEt2)2]
[l]. Treatment
I (2). The complex displays a cubane type
structure but with one less PtMeg vertex, as revealed by an X-ray analysis [2]. 0010-8545~95609.500 1995 .SSDloOIO-8545(95)0120&0
Elsevier Science
of the
in methanol afforded the
S.A. All rights reserved
432
P.K. Byers/Coordimtion
Chemistry Reviews 146 (1995) 431-450
(1) ER
No
3
N G
N>
0
-
“0
(2; R=CH2CH2NHEt2)
A novel fetrakis(arylalkyltazenido) complex [C&5NNN(CH2)5CH3]4Pt crystal X-ray crystallography
derivative
of platinum(W)
(3) was characterised
has been reported.
by 3tPt NMR spectroscopy
[3]. The first crystal structure of a platinum(IV)-cyclobutane
The
and single bearing
an electron withdrawing aldehyde functionality (4) has been described [4].
(4)
(3; Rt= (CH215CH3, R2=C6H5)
Electrospray
mass spectra
have been obtained
for a variety
of organo-platinum(IV)
compounds containing polydentate N-donor ligands. In every case the intact ion was observed as the base peak at low ion source energies [5]. The compounds shown to be isomorphous
Cs2[MC16] (M = Rh, Pt, Ir) have been
by powder diffraction [6].
12.2
PLATINUM(II)
12.2.1
Complexes withphosphine donor ligands
The dinuclear, double-bridged Bu, SiMe3) (5) have been synthesised
acetylide complexes
[Pt(p-C=CR)(C+$5)(PPh3)]2
from rrans-[Pt(C%R)2(PPh3)2]
(R = Ph,
and cis-[Pt(CgF&(thf)zl.
Treatment of the dimeric complexes with neutral ligands (L = py, PPh3) produced the mononuclear
P.K. Byers/Coordination
species truns-[Pt(C&)(CeCR)(PPh3)(L)]. by X-ray diffraction C=CPh)(CeCPh)2]+ terminal
acetylide
[Hg(PhC=C)2]
methods
The solid state structure of (5; R = Ph) was established
[7]. The dinuclear
platinum(I1)
complexes
and [PtzQt-dppm)2(l,tC=CtBu)(C=C~Bu)Cl]+ ligands
have been prepared
or [Hg(tBuC=C)2]
433
Chemistry Reviews 146 (1995) 431450
respectively.
by reaction
[Pt2Q.t-dppm)2@-
(6) containing
bridging
of [Pt(dppm-P,P’)z]C12
The crystal structures
and with
of both complexes
were
reported [8].
(5)
(6)
Reaction of [Pt2(C6F5)&t-X)$-
(X = Cl, Br, I) with dppm at room temperature
affords
[(C&)2XPt(p-dppm)PtX(C&)#-
as the kinetic products. Subsequent reaction of these di-anions
with AgC104 gave the mono-anions
(7). The bridging system in these complexes
is exceptionally
stable, and was not cleaved by anionic (X-) or neutral ligands (e.g. py, PPh3) [9]. Symmetrical unsymmetrical by reaction
dppm-bridged of compounds
[PtR’Cl(cod)],
platinum(I1) complexes
of the form [PtR(dppm-P,P’)(dppm-P)1+
respectively.
In a similar
[PtPdRMe(p-Cl)@-dppm)z]PFg P,P’Ndppm-P)l+
series
and
(8) have also been prepared, in this instance
of reactions,
with [PtRCl(cod)]
the mixed
metal
were obtained upon addition of [PdMeCl(cod)]
and
complexes
to [PtR(dppm-
1101.
0 Ph P-PPh c
2
I
-
I JR’
bc
f
I
Ph2pY/PPh2 (8)
(7)
M=Pd, Pt, R=Me, Et, Ph R’=Me, Et, Ph
The formylketenyl
platinum
complex
rrans-[PtH(ql-C(CHO)CO)(PCy3)2]
acids to cleave the Pt-C bond and generate the species C3H2O2, which is subsequently an excess of the starting material. The reaction gave rise to trans-[PtH(QH304)(PCy3)2] C6H304 established
is an a-pyrone
[ 111.
ligand
o-bonded
to platinum;
the solid state structure
reacts with trapped by (9), where of (9) was
434
P.K. B,vers/Coordination
Chemistry Reviews 146 (IYYS) 431450
(9) The reaction of (2-propenyl)bis(triphenylphosphine)platinum(II) organic substrates has been investigated. the vinylcarbene
Alkynols
triflate with unsaturated
(3.butyn- l-01 and (+)-4-pentyn-2-01)
species (lo), whilst reaction with nitriles (acrylonitrile
affords the N-bound nitile complexes
produce
and ethyl cyanoacetate)
(11). Reaction with methyl- and ethyl acrylates, on the other
hand, results in the formation of the chelated compounds
(12); the structure of (12; R = Me) was
determined using X-ray diffraction [12].
RCN\
JPPh3 Pt f
Ph,P (lo+; R=H, Me)
(12’;
(II+)
Insertion reactions of isocyanides
R=Me, Et)
into the M-C bond of (o-allenyl)platinum(II)
complexes
have been reported. When the R groups of the allenyl ligand are small, new (metallovinyl)ketenimine compounds groups
the
rrans-[PtX( insertion
[Pt( C(H)=C=CRR’] phosphirene
C(CRR’)(CH=C=NR”)}(PPh3)2] of
the
isocyanide
(CNlBu)(PPhg)2]Br
is
hindered
and
ionic
in which novel dimeric platinum(U)
(15) result from Pt-Cl bond insertion and phosphirene
Ph
(13)
sterically
results [ 131. A new type of ligating behaviour
ring system (14) has been described,
phosphane complexes
(13) are formed, whilst with large R
(14)
transof the chloro-
ring opening [14].
Ph
Ph
(15)
P. K. Byers/Coordimtion
Dichloroplatinum(I1) diazo-compounds
Chemistry
complexes
Reviews
containing
to give Pt-Cl insertion
products.
chelating
similar series of reactions, [PtCl#,R-skewphos)] to give mono-insertion
43.5
431450
his-phosphine
ligands react with
Thus, [PtClz(S,S-skewphos)]
Me3SiCHN2 to give [PtCl(S-CHClSiMe3)(S,S-skewphos)] COzMe]
146 ( 1995)
reacted
with high diastereoselectivity
with
[ 151. In a
reacted with RCHN2 {R = SiMe3, P(O)(OMe)z, (R)
products (16) in which
stereochemistry
is preferred
for the
newly created chiral centre [ 161.
Ph2
‘\
/”
RCHN,
fPf\,
,
:h,
(16) Acetylenes,
RGCR
(R = Ph, Pr), insert into the Pt-Si bond of nuns-[PtX(SiMe3)(PEt3)2]
(X = Br, I) to give trons-[PtX[C(R)=C(R)SiMe3)(PEt3)2]; [PtX(C(Ph)=C(Ph)SiMe3)(PEt3)2]
silyene complex of platinum, trans.[Pt(H) cis-[Pt(H)( Si(SEt)3(PCy3)2]
the structure
was determined by X-ray crystallography
of rrans-
[17]. A Fischer-type
[ =Si(SEt)z) (PCy3)2]BPh4 (17), has been prepared from
upon reaction with Me3SiOTf and NaBPhq. The solid state structure
of the silyene complex was reported [ 181.
(17) The syntheses
of two series of cyclopentadienyl
account, reaction of [Pt(OTQ(P-P)] compounds
[Pt(rlS-CsHS)(P-P)]OTf
compounds
[Pt(r15-CSH4R)(Ph)(L)]
treatment of [Pt(Ph)@t-OH)(L)]2
complexes
have appeared.
In the first
(P-P = dppm, dppe, dppp) with Tl(C5H5) to produce the ionic was described
[19]. In the second
report,
(Y = H, Me; L = PCy3, PPh3) were obtained
with cyclopentadiene
complexes of the type cis-[Pt(Ar)2(PPh3)2]
or methylcyclopentadiene
the neutral directly on
[20]. A range of
(Ar = aryl group) with substituents of different van der
Waals volumina and electronic character in both ortho-positions
of each platinum bonded phenyl
ring have been synthesised, and studied with respect to substituent influences on their photochemical reactivity [2 11. The trans-spanning [PtMeCl(cod)]
ligand l,%C&(CHzPPh2)2
undergoes
or [PtC12(cod)] to give (18; X = Cl), containing
cyclometallation
with either
the ligand bound to platinum in a
P.K. Byers/Coordination
436
Chemistry
Reviews
146 (1995)
431450
P,C,P’-tridentate fashion. Successive treatment of (18; X = Cl) with AgBF4 and KOH gives (18; X = OH) which reacts with CO to produce the hydroxycarbonyl (18; X = C02H). The solid state structure of the hydroxycarbonyl species was determined using X-ray diffraction methods [22].
I X (18; X=Cl, OH, CO,H) Treatment of rt-ally1 platinum(I1) complexes bearing a methoxymethoxy 2-position
with base gives oxodimethylmethane
complexes
group at the
(19) in contrast to 2-hydroxy
substituted ~-ally1 complexes via acidic hydrolysis (20) [23]. A versatile route to 2-substituted rtally1 complexes, e.g. (21), from addition of hard and soft nucleophiles to the cationic T$-propargyl complex (22) has been described [24].
(21; R=OMe, SPh, OAc)
(22)
A series of dinuclear pyrazolato-bridged platinum(I1) complexes of the form [Pt@%(pL)2(PR3)2] @IL = pz, 3,5-Me2pz; PR3 = PEt3, PMezPh, PMePh2) have been prepared by reaction of the corresponding acetate-bridged analogue with HL. A single crystal structure analysis of a representative complex, [Pt$l2(p-pz)2(PMe2Ph)2], was also reported [25]. In a similar account, the synthesis of a second series of pyrazolato-bridged platinum(I1) dimers was described. Thus, treatment of [Pt2(Ar)2(p-C1)2(PR3)2] (Ar = Ph, CgHqMe-4, C4H3S-2; PR3 = PBu3, PMezPh, PMePh2) with HL (L = pz, 3,5-Mezpz, 3,4,5,-Me3pz) and NaOH gave [Pt2(Ar)2(~-L)28R3)21(23) L-4.
P.K. Byers/Coordituzrion
Chemisfry Reviews 146 (1995) 431450
437
R1=R2=H, (23)
R’=R2=Me, R’=Me, R2=H
Reaction of cis-[PtC12(dmso)2] with Ph2Ppy gave as the main product cis[PtCl2(Ph2Ppy)(dmso)], in which Ph2Ppy is ql-bonded through phosphorus to platinum. However, treatment of cis-[PtC12(Ph2Ppy)(dmso)] with [PtMe2(dmso)2] gave the dinucleax platinum(II) compound [MeClPt(p-Cl)@-Ph2Ppy)PtMe(dmso)] (24) and the Pt(I)-Pt(1) dimer [Pt2Cl&Ph2Ppy)d; both were structurally characterised by an X-ray diffraction study [27].
(24) The preparation
and characterisation
(by X-ray diffraction
and multinuclear
NMR
spectroscopy) of mono- and bis-platinated derivatives of two diaziridines (25) has been reported [28]. Reaction of l,S-PhqP2NqSe2 with [PtC12(PEt3)2] produced the ql-N-bonded [PtC12(PEt3)ln(l,5-PhqPZNqSeZ) [n = 1; 2 (26)] [29]. Et,P \ P/’ Cl/
PV’,
,NNs,e’N, PPh2 N’S
eNN’
adducts
438
P.K. Byers/Coordination
Chemistry Reviews 146 (1995) 431-450
Treatment of [PtX2(P(CH2OH)3)2] H20
gave three
species,
which
OH)2( P(CH2OH)3)4]2+
were identified
and [Pt3@-OH)3
[Pt(OH2)2{P(CH20H)3)2]2+ tP~2U’W20W3)212+
(X = Cl, Br) with AgY (Y = NO3, BF4, PFe, ClO4) in as [Pt(OH2)2(P(CH20H)3)2]2+,
( P(CH20H)3)6]3+.
The mononuclear
reacted further with N-donor ligands to afford complexes of the form
(L2 = 2py, bpy, phen) ]301.
A series of cationic platinum(I1) complexes
[PtCl(dppe)(OC(R)CH(AsPh3))1BF4
Ph, OMe) (27) in which the carbonyl stabilised arsonium ylides are coordinated have been described
[Ptz(pLproduct
[31]. Reaction of cis-[PtClz(PPh&]
(R = Me,
to the metal centre
with dialkyl malonate in the presence of
Ag20 gave new platinalactone complexes (28), via a cyclisation reaction [32].
0
(28; R=Me, Et)
(27) The
crystal
monothioacetylacetonate)
structures
of the
complexes
[Pt(Et)(P-dik)(PPh3)]
(P-dik
= acac,
have been determined, and compared to those for [Pd(Me)@dik)(PPh&]
[33]. In a series of related papers, the preparation and charactetisation
of bis(phosphine)platinum(II)
complexes containing group 16 ligands has appeared [34-361. Thus, for example, [Pt(EPh)2(dppe)] (E = 0, S) have been prepared PhSH/Bu$JH,
respectively,
[Pt(C$I&dppe)]
by reaction
of the parent chloro-complex
while [Pt(SePh)z(dppe)]
[34]. The ability of complexes
other metal species was demonstrated
was formed by oxidative addition of Ph2Se2 to of this type to act as didentate ‘ligands’ towards
[35,36]. For example, cis-[Pt(SC&)2L2]
2PPh3) when treated with cis-[M(C&)2(th&] dinuclear compounds
with NaOPh or
(L2 = dppm, dppe,
(M = Pd, Pt) yielded the geminal homo- or hetero-
(29) [36]. C6F5 c6F”\M
AptJL
C6F5’
\S’
y c6F5
L
(29; M=Pd, Pt)
The complex [Pt(H2dmsucc-S,S’)(L-L)] 1-diphenylarsino-2-diphenylphosphino structure
of [Pt(Et2dtc)(P2P’)]BF4
been established
(H4dmsucc = dimercaptosuccinic
acid; L-L = dppe,
ethane) (30) have been prepared and characterised (Et2dtc = S2CNEt2; P2P’ = PhP(CHZCH2PPh&)
using X-ray diffraction
techniques.
The short non-bonding
distance
[37]. The (31) has between
platinum and sulfur (2.753(3) A) indicated the possibility of some interaction between the two atoms in the solid state [38].
P.K. Byers/Coordination
439
Chemistry Reviews 146 (1995) 431-450
CO,H
CO,H
Phz (30; E=As, P) The
platinum(O)
dibenzothiophene characterised
complex
[Pt(PEt3)3]
to give the compound
by NMR spectroscopy
state structure of cis-[PtC12(SEt2)(P(CH2CH2CN)3]]
umbrella
relative
‘Bu3CeHz)TeLi*3thf platinum(B)
into the C-S bond
to platinum
of
[39]. The solid
and rruns-[PtCl2(P(CH2CH$N)3)2]
In the latter, the P(CH$HzCN)3 [40]. Reaction
or (2,4,6-iPr3CeH2)TeLi*3thf
tellurolates;
(reversibly)
a Pt-S-C linkage. The new complex was
and an X-ray crystal structure determination
been determined crystallographically. an ‘inverted
inserts
(32) containing
have
ligands were found to form
of cis-[PtC12(PPh3)2]
gave the corresponding,
for example (33) whose structure was established
with (2,4,6air stable, cis-
using X-ray diffraction
1411.
(32)
cis-(34;
(33; R=‘Bu)
A convenient
one step method
for the synthesis
of dinuclear
R=CH,OH)
platinum(I1)
phosphine
complexes
has been reported. The procedure involves direct reaction of PtC12 and the appropriate
phosphine
in p-chlorotoluene
equivalents
to
[PtCl2(P(CHZOH)3]2]. [PtCl(P(CH20H)3]3]Cl, assigned
as
[42]. Addition of 3 equivalents
K2[PtC14]
results
gives, amongst
In
the
other things,
The new meso-ligand
of P(CH2OH)s of
the
to Na[PtCle] or 2
platinum(I1)
of P(CH20H)s
to this complex
presence
of
further
the bis(chelate)
gives
(34) [43]. The related phosphine
P(CHzOH)3,
salts trans-
and cis-
ligand Ph2PCH2OH
the structure of which has been
[44].
(R*,S*)-2,3-bis(diphenylphosphino)butane
(achiraphos)
and used to prepare the prochiral complex [PtC12(achiraphos)]. Displacement
the enantiotopic
complex
gives an unstable species tentatively
to give cis-[PtC12(Ph2PCHzOH)2],
determined by X-ray crystallography
synthesised
formation
while reaction with 2 equivalents
[Pt( (HOCH2)2PCH20P(CH20H)2)2]Clz with [PtClz(cod)]
the
Addition of a further equivalent
[PtCl(P(CH2OH)3)4]Cl.
[PtCl (P(CH2OH)3)4]Cl
reacted
in
chlorine atoms with [lR-(la,2P,5a)]-diphenylmenthylphosphine
has been of one of
(R-PMenPh2)
P. K. Byers/Coordination
440
and
subsequent
treatment
with
Chemistry Reviews
NH4PFe
gave
146 (I 995) 431-#50
diastereomeric
complexes
of the form
[PtCl(achiraphos)(R-PMenPh2)lPFe
(35). The solid state structure of one of the epimers has been
determined by X-ray crystallography
[45].
(35) Preparation
of the diphenyl(phenylethynyl)phosphine
For (36) intramolecular
coupling of the phosphinoacetylene
and from (37; X = Cl) the free unsymmetrical
diphosphine
complexes
(36) has been reported.
ligands occurs on heating to form (37), [o-Cl&Ito(PPh2)2],
generated by this
coupling step, has been isolated [46].
cl\
Ph
,:“‘=
c,/PtKIJh
E
Ph
2
(36) The series of complexes
(37) [PtXx’(r$(PPh2)$IH}]
(X = X’ = Cl, C&;
X = Cl, x’ = C&)
have been prepared, and 3tP( lH} NMR spectra indicate that one of the phosphorus triphosphine
ligand remains
N(Ph)PPhz
has been synthesised,
dimethylplatinum(II)
uncoordinated
[47]. The new diphosphine
and treatment
with [PtMez(cod)]
atoms of the
PPhZCH$JtBu)=Naffords
the expected
species (38) [48].
Ph2 “\pt/p\
R,P/*
YJN i’h,
tih (38) Treatment
(39) of cis-[PtC12(PR3)2]
with dppa {Ph2PN(H)PPh2)
(PR3 = PMe3, PMeTPh, PMePh2, P(nBu)g, PPh3, PEt3j
afforded the cationic complexes
[PtCl(PR3)(dppa)]Cl
(39), whilst
P.K. Byers/Coordimtion
reaction
of [PtC12(dppe)]
[PtCl(PMe2Ph)(dppa)]Cl,
with dppa gave [Pt(dppa)(dppe)]C12. [PtCl(P(nBu)3](dppa)]Cl
by X-ray crystallography phosphorus
and in each instance,
complexes
441
The molecular
and [Pt(dppa)(dppe)]Clz
structures
[PtC12{ RN[P(OPh)&]]
of
have been determined
reveal dppa acting as a chelate through
atoms [49]. The reaction of [PtC12(cod)] with RN[P(OPh)2]2
similar P,P’-chelate
both
(R = Me, Ph) affords
[50].
Complexes with nitrogen donor ligands
122.2
Reaction of organomercury complexes
ChemisrryReviews I46 (1995) 431&450
halides HgR’Cl (R’ = Me, Et, tBu, Ph) with the platinum(O)
[Pt(dmphen){ (Z)-RO$CH=CHC@R}]
(dmphen = 2,9-Me2-l,lO-phenanthroline;
R =
Me, Et, ~Bu) produced 5 coordinate platinum@) compounds of the form [PtCl(HgR’)(dmphen){
Q-
R02CCH=CHC02R)]
(40); the solid state structure of (40; R = Me, R’ = Me) was established
using X-ray diffraction
methods [Sl]. A second series of Scoordinate
general formula
[PtR(Cl)(N-N)(YC=CY)]
platinum@)
complexes
CH2Cl; R = Me, 4-MeOC&),
e.g. (41). have been prepared by treatment of [PtR(Cl)(N-N)]
alkynes.
alkyne:[PtMe(Cl)(dmphen)]
Using
a
1:2
[Pt2Me2(C1)2(YC=CY)(dmphen)]
ratio
were isolated, and for the but-2-yne
structure determined crystallographically
of
(N-N = didentate N-donor ligand; Y = CF3, COzMe,
dinuclear derivative
with
species the molecular
[52].
-/yCF3 / 3c
Cl
(40) Cyclometallation with platinum(I1) CH$eHg](lt-OAc)]2
reactions of N-benzyl and N-(phenylethyl)-cl-benzoylbenzylideneamines
salts have been reported, (42) established
2,9-diphenyl-l,lO-phenanthroline) (43) is substitution cyclometallated
(41)
and the structure
of [Pt{CeH4(CeH5C=O)C=N-
[53]. Reaction of [Pt(MeCN@+
gave the cyclometallated
labile, and can be replaced
with dpphen (dpphen =
complex (43). The acetonitrile ligand in
by nitrogen
derivative [PtLCl] (HL = &Bu-2,2’-bipyridine)
bases [54]. The synthesis has been reported [55].
0
0
L (42)
NCMe (43)
I
of the
P.K. Byers/Coordination
442
The mixed alkylplatinum(I1)
Chemistp
complex [Pt(CF3)(CH3)(nbd)]
(L2 = e.g. tmen, 2py, bpy) to afford the corresponding MeCN, [Pt(CF$(CH3)(MeCN)2]
Reviews 146 (1995) 431-450
complexes
reacts with neutral ligands L2 [Pt(CF3)(CH$(L2)],
whilst with
is formed in equilibrium with starting materials [56]. The kinetics
of CN- substitution at platinum@)
in the series cis- and trans.[PtC12(am)2]
(am = e.g. MezNH, py.
4-CNpy, 4-Clpy, 2-Mepy) has been investigated for the slow step in equation (i) [57]. [Pt(CN)2(am)2]
+ CN- +
Treatment of cis-[Pt(C&)2(thf)2]
(i)
with 2-benzyl pyridine gave cis-[Pt(C&)2(PhCH2py)]
(44), which in the solid state, as established platinum interaction.
[Pt(CN)3(am)]-
by X-ray diffraction,
exhibits
a weak $-benzyl
Subsequent reaction of (44) with CO yielded [Pt(C#s)2(PhCH2py-N)(CO)]
which did not contain a Pt-benzyl interaction [58].
E Q
xptyF” / C6F5
0
(44)
Three platinum(I1)
complexes
molecular structures determined
of l,l’-biisoquinoline
ligand was found to be didentate, whilst in the complexes biisoquinoline
adopted
[PtC13(NCR)]-
and cis- and truns-[PtClz(NCR)2]
and mixed amide-nitrile platinum. intermetallic
a unidentate
complexes,
The complexes interaction.
(biq) have been prepared and their
using X-ray crystallography.
bonding
mode
In one of these, [PtClz(biq)] (45) the
[Pt(biq)(L)3] (L = py, 4-NMe2py)
[59]. Mono-
(R = ~Bu, Me, Ph) hydrolyse
For example,
of two platinum(I1)
monomeric
cis-[PtC12( HN=C(OH)lBu)&
distance of 3.165(l) A [60].
(46)
l,l’-
complexes
to amidate-amide
with the amide ligands in the enol form and N-bound
are composed
(45)
and bis-nitrile
to
units, with a Pt-Pt
(46) possesses
a Pt-Pt
P.K. Byers/Coordination
Chemistry Reviews
Reaction of the complex [PtCl(@U!zH&tmen)]+ 3,6-his-(dimethylamino)acridine) molecule
by an ethylene
endocyclic
146 (1995)
443
431450
with acridines (3,6-diaminoacridine
and
afforded complexes in which the metal is linked to the polycyclic
chain. For 3,6-his-(dimethylamino)acridine
nitrogen to give (47) whilst for 3,6-diaminoacridine
attack occurred
at the
attack occurred at the exocyclic
aminic groups to afford (48); the structure of the former was established
using X-ray diffraction
[611. N
fr
(48”)
(47+)
Treatment
of cis- and trans-[PtC12(NCR)2]
tBu) with 2 equivalents
of [OCH2CH$l]-
rrans-[PtC12(N=C(R)OCH$ZH2)2] [Pt(terpy)L’]“+ spectroscopic
(R = 4-MePh, 4-CFsPh,
affords the bis(A2-1,3-oxazoline)
2-MePh, Et, nPr, jPr, derivatives
in high yield [62]. A series of platinum-terpy
cis- and
complexes
(L’ = Cl, Br, I, N3, SCN (n = 1); L’ = NH3 (n = 2)) have been prepared and their and emission
range of complexes
properties
studied [63]. The 1H NMR and vibrational
of the general formula [PtCl2(am)] (am = cycloalkylamine
spectra for a
CnH2,,_tNH2; n =
348) have been reported [64].
12.2.3
Complexes with sulfiir group donor ligands
The series isoquinoline-N-oxide,
of complexes
Z&se’s salt. Subsequent
reaction
afforded frans-[PtC12(L’)(4-MeQNO)] An account detailing tridentate
ligand
trans-[PtC12(C2Hq)L]
4-ClQNO, 2-MeQNO, 4-MeQNO)
(L = quinoline
N-oxide
(QNO),
have been prepared by addition of L to
of [PtC12(C2H4)(4_MeQNO)]
with L’ (L’ = CO, PPh3, py)
[65].
the synthesis
of a range of complexes
1,4,7-trithiacyclononane,
[9]aneSg
(49),
containing
has appeared.
the potentially The complexes
[PtRR’( [9]aneS3]] (R = R’= Me, Et, CH2CMe3, CHzSiMe3, Ph; R = Me, R’ = CH2SiMe3; R = Cl, R’= CHzSiMe3) were prepared by displacement [PtPh:!(]9]aneS3]1
of cod or nbd from appropriate precursors, and for
the molecular structure was established
by X-ray crystallography
[66]. In two
444
related
P.K. Byers/Coordi.mztion
reports,
the complexes
Chemistry Reviews 146 (1995) 431450
[Pt( (50))212+ [67] and [Pt((Sl)]]2+
[68] were prepared
and
structurally characterised using X-ray diffraction methods.
l-7
s-
rl
c,:,s_,9qj1 PlmeS3
[lOlaneS
(4%
[12]ane!&
(50)
The synthesis, characterisation,
X-ray structure determination
(51) and emission spectroscopy
of
(52) and (53) has been reported. Both complexes were obtained upon reaction of [PtCl;?(cod)] and the corresponding [Pt(&C)(py)]
dianionic
dithiolate
and [Pt($C)(PMe3)]
salt [69]. The platinum(II)
complexes
[Pt($C)]2,
(54) (S2C = 1,3-imidazolidinyl-N,W-hir(2-benzenethiolate)
have been prepared and fully characterised [70].
QNy+ S-pt-S
I
PMe, (54)
12.2.4
Complexes with mixed donor ligands
The new P,N-didentate prepare
the complexes
Ar)N(SiMe&)(PEt$l NJ-chelating spectroscopy
ligand (55), derived from valine, has been synthesised
[PtX2(55)]
(X = Cl, I) [71]. Reaction
(Ar = 4-MeCgHq) with PhSeCl was reported to give (56), containing
ligand PPhzN(H)C(Ar)=N(H). and X-ray crystallography
The structure of (56) was established
[72]. The dinuclear platinum compounds
have been isolated from the reaction of cis-[PtCl2(dmso)(PPh2py)] cis-[PtMg(dmso)2];
and used to
of trans-[PtCl2(PPhzNC(4the
using NMR (57) and (58)
with an equimolar quantity of
both complexes were the subject of an X-ray diffraction study [27].
P.K. Byers/Coordination
Chemistry Reviews 146 (1995) 431450
(56; Ar=4-MeC6H4)
Ph,P
Jo
Ph,P
i,Mei,“e s+
/
“t Pt-c
+
tc PPh2
c I--Pt-
I/‘t’ Cl
s
The ligands PhzPN(Ph)PPhz(=E) [PtClz(P-E)]
(E = S, Se) (P-E) have been used to prepare the mixed
(59), and for E = S the solid state structure has been established
[73]. The neutral, dimeric complexes
[(Pt(C&)(ttSPPh2)(PR3))2]
cationic complexe [Pt(SPPh2)(PPh+]C104
(PR3 = PPh3, PPh2Et) and
have been reported. For the former the [SPPh&
is present as a P,S-bridge whilst in the latter it adopts a P,S-chelating Treatment
of the chloro-bridged
the anion [C(PPh2)(P(S)Ph2)2](60) and [Pt(MeOcod)( isomers
complexes
of [PtClz(E-S)]
ligand
bonding mode [74].
[Pt$4(PEt&]
affords the complexes
C(PPh2)(P(S)Ph2)2-P,s)l,
[75]. The synthesis
complexes
I
(58)
(57; S=dmso)
donor complexes
/Jo
and [Pt2Clz(MeOcod)21
with
[PtCl(PEt3)(C(PPh2)(P(S)Ph2)2-P,S]] as a mixture of cis- and trans-
respectively,
(E-S = (+)Ph2ECHZCH$(O)Me
(E = P, As))
has been reported. In both cases, the ligand acts as an E,S-didentate
ligand, and M-O
bonds are not involved [76].
“\pt/S“/iph2
\pO’\
EtgPf
Ph2 (59) Reaction monomeric mono-anionic
of [Pt(C6F5)2(lt-C1)J22-
complex
[Pt(CtjFs)2(C5bNS)]-,
Fr2’
(60) with [CgHqNS]possessing
(pyridine-2-thiolate)
affords
the
a [N-S]- chelate. Upon reaction of this
complex with PPh3 the species [Pt(C&+(C5&NS)(PPh3)]-,
possessing
the ligand
446
P. K. Byers/Coordination
in a monodentate
S-binding
Chemistry Reviews 146 (1995) 431450
mode is obtained
[77]. The crystal structures
of four platinum(I1)
complex cations (61) containing the organic ligand 2,6-bis(methylthiomethyl)pyridine determined
by X-ray diffraction
NSPh] with [Pt(Q&)(PPh3)2]
have been
[78]. Reaction of rruns-[PhSNC(MeCeH4)N=NC(MeC6H& gave the platinum(II)
complex (62) in which the ligand is bonded
in a NjV’,S-tridentate fashion [79]
0
A 0
N
S-p*u-s+
I
X
(62; Ar=4-MeC,H,)
(61; X=CI, Br, SCN)
The thioether
and sulphinyl
azo-benzene
complexes
(63) and (64), respectively,
insert oxygen into the Pt-0 bond when treated with m-chloroperbenzoic containing the OJ,S-donor
slowly
acid to produce species
set [80].
o\ 0
Pt
N*
Nf
7
‘t
0
VR 0
o(63)
Treatment analogous
of platinum
palladium(U)
(64)
salts with L2- (65) affords
salt, [Pd2(L)12+,
macrocycle to be planar with inter-molecular
the complex
the solid state structure x-ring stacking [81].
(65)
[Pt2(L)12’.
showed
For the
the dinucleating
P.K. Byers/Coordinution
12.3
447
Chemistry Reviews 146 (1995) 431ASO
PLATINUM(I)
The first example of a p-parallel ligated phospha-alkyne [Pt2Cl&-dppm)2Q.t-IBUCP)] NMR spectroscopy
has been reported for the complex
(66). The structure of the molecule was elucidated by 3lP and 195Pt
[82].
‘“.9/‘\r
PPh2
p-c
c I-y-
I
t
pI Ph2pvPPh2 (66;
Reaction of [Pt$&(dppm)2] afforded the new compounds
R=‘Bu)
with 2 L (L = quinoline, N-methylimidazole,
gave [Pt2(dppm)2(L’)Cl]+. For (67; L = quinoline, N-methylimidazole) solid state structure
4-lbutylpyridine)
[Pt2(dppm)2L212+ (67), whilst reaction with L’ = 2,4,6-Me3pyridine
was determined
crystallographically,
2.615(l), 2.580(l) and 2.627(2) A, respectively,
and [Pt2(dppm)&‘)Cl]+
and the Pt-Pt distances
the
found to be
thus establishing the presence of a Pt-Pt bond [83].
L*Pt-Pt-L
L=
t
t ‘B u
Ph2pVPPh2 (67”)
12.4
PLATINUM(O)
Reaction of 1-bromocycloheptene tBuOK in the presence of [Pt(PPh&] of the corresponding thf in the presence
or a mixture of l-, 2- and 3-bromocycloheptamenes
led to the predominant
formation of Pt(PPh$z
with
A-complexes
cyclic allenes, e.g. (68). In contrast, reaction of the same halides with LDA in of [Pt(PPhg)g]
gave exclusively
Pt(PPh3)2 complexes
of the corresponding
cyclic alkynes, e.g. (69) [84]. The preparation (C02Et)=CH(C02Et)
of [Pt(trans-CH(COzEt)=CH(CO2Et)}(PPh3)2]
and [Pt(cis-CH-
1(PPh3)2] has been described. The complexes were prepared by reaction of
]Pt(q2-CH2CH$(PPh3)2]
with frans- and cisCH(C02Et)=CH(C02Et),
[Pt(rruns-CH(C02Et)=CH(CO2Et)](PPh3)2]
the structure was determined
1851. The platinum(O) dimer [Pt&-CO)(CO)2Q.t-dppm)2]
respectively,
and for
from an X-ray analysis
(70) has been prepared from [Pt$12(p-
P. K. Byers/Coordimtion
448
dppm)2] via NaBH4 reduction [Pt2(p-dppm)3]
Chemistry Reviews 146 (1995) 431450
under a CO atmosphere
and by substitution
of a dppm ligand in
with CO [ 861.
d”““”
o+Pt(PPh3J2
ph;zk$p;h2 2
(68)
(69)
2
(70)
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ELSEVIER
431-450
12.
Platinum
Peter
1993
K. Byers
CONTENTS INTRODUCTION . .... . .. .... .. ... .. .. .. .. .. . .... .. .. ... .. .. .... .. . ..__......... .... .. .. .._...... .. . .. .. .. .... . .. .... 12.1 PLATINUM(IV) .. .._...... .... .. .. .... .. ... .... .. .. .... .. .. ... .. .. .... .. .. .. .. .. ..... .. .... .. .. .... . .... .. .. 12.2 PLATINUM(I1) .... .. .. .. .. .. .. .... . ... .... .. .. .... . . .... .. .. .... .. .. .... .. .... .. .. ... . .. .... .. .. .. .. .. .... .. 12.2.1 domplexes with phosphine donor ligands ................................ 12.2.2 Complexes with nitrogen donor ligands .................................... 12.2.3 Complexes with sulfur group donor ligands ............................. 12.2.4 Complexes with mixed donor ligands ....................................... 12.3 PLATINUM(I) ................................................................................................ 12.4 PLATINUM(O) ............................................................................................... REFERENCES ..........................................................................................................
431 431 432 432 441 443 444 z:: 448
INTRODUCTION The coordination
chemistry of platinum reported during the year 1993 has been reviewed.
Although this account does not intend or claim to be comprehensive,
examples have been selected to
represent important features. Only the primary journals are covered and were searched using both platinum (and related) as a keyword and being present in the title. The review covers the chemistry of platinum in its 0 + +4 oxidation states, but does not include the catalytic activity of platinum complexes, nucleoside
complexes
bases. Classification
atom. For complexes donors
containing
have priority
only Pt-C bonds or complexes
of the complexes
is according
containing
to the oxidation
nucleotide
or
state and donor
containing mixed donor sets the priority ordering P>N>S applies, and neutral over charged
donor atoms; mixed
donor didentate
ligands
are treated
separately. PLATINUM(IV)
12.1
Reaction
of [PtMez(phen)]
[Pt(Me)z(ER)z(phen)]
SMe, SPh, SePh) gives
(1) as a mixture of truns- (major) and cis- (minor) isomers. For (1; ER =
SePh) the solid state structure platinum(IV)
with RE-ER (ER = OH, OC(O)Ph,
was determined
iodide [PtMej(p-I)]4
by X-ray crystallography
with the aminothiol HS(CH2)2NEt2
trinuclear species [(PtMeg)s( (p-I), p-S(CH2)2NHEt2)2]
[l]. Treatment
I (2). The complex displays a cubane type
structure but with one less PtMeg vertex, as revealed by an X-ray analysis [2]. 0010-8545~95609.500 1995 .SSDloOIO-8545(95)0120&0
Elsevier Science
of the
in methanol afforded the
S.A. All rights reserved
432
P.K. Byers/Coordimtion
Chemistry Reviews 146 (1995) 431-450
(1) ER
No
3
N G
N>
0
-
“0
(2; R=CH2CH2NHEt2)
A novel fetrakis(arylalkyltazenido) complex [C&5NNN(CH2)5CH3]4Pt crystal X-ray crystallography
derivative
of platinum(W)
(3) was characterised
has been reported.
by 3tPt NMR spectroscopy
[3]. The first crystal structure of a platinum(IV)-cyclobutane
The
and single bearing
an electron withdrawing aldehyde functionality (4) has been described [4].
(4)
(3; Rt= (CH215CH3, R2=C6H5)
Electrospray
mass spectra
have been obtained
for a variety
of organo-platinum(IV)
compounds containing polydentate N-donor ligands. In every case the intact ion was observed as the base peak at low ion source energies [5]. The compounds shown to be isomorphous
Cs2[MC16] (M = Rh, Pt, Ir) have been
by powder diffraction [6].
12.2
PLATINUM(II)
12.2.1
Complexes withphosphine donor ligands
The dinuclear, double-bridged Bu, SiMe3) (5) have been synthesised
acetylide complexes
[Pt(p-C=CR)(C+$5)(PPh3)]2
from rrans-[Pt(C%R)2(PPh3)2]
(R = Ph,
and cis-[Pt(CgF&(thf)zl.
Treatment of the dimeric complexes with neutral ligands (L = py, PPh3) produced the mononuclear
P.K. Byers/Coordination
species truns-[Pt(C&)(CeCR)(PPh3)(L)]. by X-ray diffraction C=CPh)(CeCPh)2]+ terminal
acetylide
[Hg(PhC=C)2]
methods
The solid state structure of (5; R = Ph) was established
[7]. The dinuclear
platinum(I1)
complexes
and [PtzQt-dppm)2(l,tC=CtBu)(C=C~Bu)Cl]+ ligands
have been prepared
or [Hg(tBuC=C)2]
433
Chemistry Reviews 146 (1995) 431450
respectively.
by reaction
[Pt2Q.t-dppm)2@-
(6) containing
bridging
of [Pt(dppm-P,P’)z]C12
The crystal structures
and with
of both complexes
were
reported [8].
(5)
(6)
Reaction of [Pt2(C6F5)&t-X)$-
(X = Cl, Br, I) with dppm at room temperature
affords
[(C&)2XPt(p-dppm)PtX(C&)#-
as the kinetic products. Subsequent reaction of these di-anions
with AgC104 gave the mono-anions
(7). The bridging system in these complexes
is exceptionally
stable, and was not cleaved by anionic (X-) or neutral ligands (e.g. py, PPh3) [9]. Symmetrical unsymmetrical by reaction
dppm-bridged of compounds
[PtR’Cl(cod)],
platinum(I1) complexes
of the form [PtR(dppm-P,P’)(dppm-P)1+
respectively.
In a similar
[PtPdRMe(p-Cl)@-dppm)z]PFg P,P’Ndppm-P)l+
series
and
(8) have also been prepared, in this instance
of reactions,
with [PtRCl(cod)]
the mixed
metal
were obtained upon addition of [PdMeCl(cod)]
and
complexes
to [PtR(dppm-
1101.
0 Ph P-PPh c
2
I
-
I JR’
bc
f
I
Ph2pY/PPh2 (8)
(7)
M=Pd, Pt, R=Me, Et, Ph R’=Me, Et, Ph
The formylketenyl
platinum
complex
rrans-[PtH(ql-C(CHO)CO)(PCy3)2]
acids to cleave the Pt-C bond and generate the species C3H2O2, which is subsequently an excess of the starting material. The reaction gave rise to trans-[PtH(QH304)(PCy3)2] C6H304 established
is an a-pyrone
[ 111.
ligand
o-bonded
to platinum;
the solid state structure
reacts with trapped by (9), where of (9) was
434
P.K. B,vers/Coordination
Chemistry Reviews 146 (IYYS) 431450
(9) The reaction of (2-propenyl)bis(triphenylphosphine)platinum(II) organic substrates has been investigated. the vinylcarbene
Alkynols
triflate with unsaturated
(3.butyn- l-01 and (+)-4-pentyn-2-01)
species (lo), whilst reaction with nitriles (acrylonitrile
affords the N-bound nitile complexes
produce
and ethyl cyanoacetate)
(11). Reaction with methyl- and ethyl acrylates, on the other
hand, results in the formation of the chelated compounds
(12); the structure of (12; R = Me) was
determined using X-ray diffraction [12].
RCN\
JPPh3 Pt f
Ph,P (lo+; R=H, Me)
(12’;
(II+)
Insertion reactions of isocyanides
R=Me, Et)
into the M-C bond of (o-allenyl)platinum(II)
complexes
have been reported. When the R groups of the allenyl ligand are small, new (metallovinyl)ketenimine compounds groups
the
rrans-[PtX( insertion
[Pt( C(H)=C=CRR’] phosphirene
C(CRR’)(CH=C=NR”)}(PPh3)2] of
the
isocyanide
(CNlBu)(PPhg)2]Br
is
hindered
and
ionic
in which novel dimeric platinum(U)
(15) result from Pt-Cl bond insertion and phosphirene
Ph
(13)
sterically
results [ 131. A new type of ligating behaviour
ring system (14) has been described,
phosphane complexes
(13) are formed, whilst with large R
(14)
transof the chloro-
ring opening [14].
Ph
Ph
(15)
P. K. Byers/Coordimtion
Dichloroplatinum(I1) diazo-compounds
Chemistry
complexes
Reviews
containing
to give Pt-Cl insertion
products.
chelating
similar series of reactions, [PtCl#,R-skewphos)] to give mono-insertion
43.5
431450
his-phosphine
ligands react with
Thus, [PtClz(S,S-skewphos)]
Me3SiCHN2 to give [PtCl(S-CHClSiMe3)(S,S-skewphos)] COzMe]
146 ( 1995)
reacted
with high diastereoselectivity
with
[ 151. In a
reacted with RCHN2 {R = SiMe3, P(O)(OMe)z, (R)
products (16) in which
stereochemistry
is preferred
for the
newly created chiral centre [ 161.
Ph2
‘\
/”
RCHN,
fPf\,
,
:h,
(16) Acetylenes,
RGCR
(R = Ph, Pr), insert into the Pt-Si bond of nuns-[PtX(SiMe3)(PEt3)2]
(X = Br, I) to give trons-[PtX[C(R)=C(R)SiMe3)(PEt3)2]; [PtX(C(Ph)=C(Ph)SiMe3)(PEt3)2]
silyene complex of platinum, trans.[Pt(H) cis-[Pt(H)( Si(SEt)3(PCy3)2]
the structure
was determined by X-ray crystallography
of rrans-
[17]. A Fischer-type
[ =Si(SEt)z) (PCy3)2]BPh4 (17), has been prepared from
upon reaction with Me3SiOTf and NaBPhq. The solid state structure
of the silyene complex was reported [ 181.
(17) The syntheses
of two series of cyclopentadienyl
account, reaction of [Pt(OTQ(P-P)] compounds
[Pt(rlS-CsHS)(P-P)]OTf
compounds
[Pt(r15-CSH4R)(Ph)(L)]
treatment of [Pt(Ph)@t-OH)(L)]2
complexes
have appeared.
In the first
(P-P = dppm, dppe, dppp) with Tl(C5H5) to produce the ionic was described
[19]. In the second
report,
(Y = H, Me; L = PCy3, PPh3) were obtained
with cyclopentadiene
complexes of the type cis-[Pt(Ar)2(PPh3)2]
or methylcyclopentadiene
the neutral directly on
[20]. A range of
(Ar = aryl group) with substituents of different van der
Waals volumina and electronic character in both ortho-positions
of each platinum bonded phenyl
ring have been synthesised, and studied with respect to substituent influences on their photochemical reactivity [2 11. The trans-spanning [PtMeCl(cod)]
ligand l,%C&(CHzPPh2)2
undergoes
or [PtC12(cod)] to give (18; X = Cl), containing
cyclometallation
with either
the ligand bound to platinum in a
P.K. Byers/Coordination
436
Chemistry
Reviews
146 (1995)
431450
P,C,P’-tridentate fashion. Successive treatment of (18; X = Cl) with AgBF4 and KOH gives (18; X = OH) which reacts with CO to produce the hydroxycarbonyl (18; X = C02H). The solid state structure of the hydroxycarbonyl species was determined using X-ray diffraction methods [22].
I X (18; X=Cl, OH, CO,H) Treatment of rt-ally1 platinum(I1) complexes bearing a methoxymethoxy 2-position
with base gives oxodimethylmethane
complexes
group at the
(19) in contrast to 2-hydroxy
substituted ~-ally1 complexes via acidic hydrolysis (20) [23]. A versatile route to 2-substituted rtally1 complexes, e.g. (21), from addition of hard and soft nucleophiles to the cationic T$-propargyl complex (22) has been described [24].
(21; R=OMe, SPh, OAc)
(22)
A series of dinuclear pyrazolato-bridged platinum(I1) complexes of the form [Pt@%(pL)2(PR3)2] @IL = pz, 3,5-Me2pz; PR3 = PEt3, PMezPh, PMePh2) have been prepared by reaction of the corresponding acetate-bridged analogue with HL. A single crystal structure analysis of a representative complex, [Pt$l2(p-pz)2(PMe2Ph)2], was also reported [25]. In a similar account, the synthesis of a second series of pyrazolato-bridged platinum(I1) dimers was described. Thus, treatment of [Pt2(Ar)2(p-C1)2(PR3)2] (Ar = Ph, CgHqMe-4, C4H3S-2; PR3 = PBu3, PMezPh, PMePh2) with HL (L = pz, 3,5-Mezpz, 3,4,5,-Me3pz) and NaOH gave [Pt2(Ar)2(~-L)28R3)21(23) L-4.
P.K. Byers/Coordituzrion
Chemisfry Reviews 146 (1995) 431450
437
R1=R2=H, (23)
R’=R2=Me, R’=Me, R2=H
Reaction of cis-[PtC12(dmso)2] with Ph2Ppy gave as the main product cis[PtCl2(Ph2Ppy)(dmso)], in which Ph2Ppy is ql-bonded through phosphorus to platinum. However, treatment of cis-[PtC12(Ph2Ppy)(dmso)] with [PtMe2(dmso)2] gave the dinucleax platinum(II) compound [MeClPt(p-Cl)@-Ph2Ppy)PtMe(dmso)] (24) and the Pt(I)-Pt(1) dimer [Pt2Cl&Ph2Ppy)d; both were structurally characterised by an X-ray diffraction study [27].
(24) The preparation
and characterisation
(by X-ray diffraction
and multinuclear
NMR
spectroscopy) of mono- and bis-platinated derivatives of two diaziridines (25) has been reported [28]. Reaction of l,S-PhqP2NqSe2 with [PtC12(PEt3)2] produced the ql-N-bonded [PtC12(PEt3)ln(l,5-PhqPZNqSeZ) [n = 1; 2 (26)] [29]. Et,P \ P/’ Cl/
PV’,
,NNs,e’N, PPh2 N’S
eNN’
adducts
438
P.K. Byers/Coordination
Chemistry Reviews 146 (1995) 431-450
Treatment of [PtX2(P(CH2OH)3)2] H20
gave three
species,
which
OH)2( P(CH2OH)3)4]2+
were identified
and [Pt3@-OH)3
[Pt(OH2)2{P(CH20H)3)2]2+ tP~2U’W20W3)212+
(X = Cl, Br) with AgY (Y = NO3, BF4, PFe, ClO4) in as [Pt(OH2)2(P(CH20H)3)2]2+,
( P(CH20H)3)6]3+.
The mononuclear
reacted further with N-donor ligands to afford complexes of the form
(L2 = 2py, bpy, phen) ]301.
A series of cationic platinum(I1) complexes
[PtCl(dppe)(OC(R)CH(AsPh3))1BF4
Ph, OMe) (27) in which the carbonyl stabilised arsonium ylides are coordinated have been described
[Ptz(pLproduct
[31]. Reaction of cis-[PtClz(PPh&]
(R = Me,
to the metal centre
with dialkyl malonate in the presence of
Ag20 gave new platinalactone complexes (28), via a cyclisation reaction [32].
0
(28; R=Me, Et)
(27) The
crystal
monothioacetylacetonate)
structures
of the
complexes
[Pt(Et)(P-dik)(PPh3)]
(P-dik
= acac,
have been determined, and compared to those for [Pd(Me)@dik)(PPh&]
[33]. In a series of related papers, the preparation and charactetisation
of bis(phosphine)platinum(II)
complexes containing group 16 ligands has appeared [34-361. Thus, for example, [Pt(EPh)2(dppe)] (E = 0, S) have been prepared PhSH/Bu$JH,
respectively,
[Pt(C$I&dppe)]
by reaction
of the parent chloro-complex
while [Pt(SePh)z(dppe)]
[34]. The ability of complexes
other metal species was demonstrated
was formed by oxidative addition of Ph2Se2 to of this type to act as didentate ‘ligands’ towards
[35,36]. For example, cis-[Pt(SC&)2L2]
2PPh3) when treated with cis-[M(C&)2(th&] dinuclear compounds
with NaOPh or
(L2 = dppm, dppe,
(M = Pd, Pt) yielded the geminal homo- or hetero-
(29) [36]. C6F5 c6F”\M
AptJL
C6F5’
\S’
y c6F5
L
(29; M=Pd, Pt)
The complex [Pt(H2dmsucc-S,S’)(L-L)] 1-diphenylarsino-2-diphenylphosphino structure
of [Pt(Et2dtc)(P2P’)]BF4
been established
(H4dmsucc = dimercaptosuccinic
acid; L-L = dppe,
ethane) (30) have been prepared and characterised (Et2dtc = S2CNEt2; P2P’ = PhP(CHZCH2PPh&)
using X-ray diffraction
techniques.
The short non-bonding
distance
[37]. The (31) has between
platinum and sulfur (2.753(3) A) indicated the possibility of some interaction between the two atoms in the solid state [38].
P.K. Byers/Coordination
439
Chemistry Reviews 146 (1995) 431-450
CO,H
CO,H
Phz (30; E=As, P) The
platinum(O)
dibenzothiophene characterised
complex
[Pt(PEt3)3]
to give the compound
by NMR spectroscopy
state structure of cis-[PtC12(SEt2)(P(CH2CH2CN)3]]
umbrella
relative
‘Bu3CeHz)TeLi*3thf platinum(B)
into the C-S bond
to platinum
of
[39]. The solid
and rruns-[PtCl2(P(CH2CH$N)3)2]
In the latter, the P(CH$HzCN)3 [40]. Reaction
or (2,4,6-iPr3CeH2)TeLi*3thf
tellurolates;
(reversibly)
a Pt-S-C linkage. The new complex was
and an X-ray crystal structure determination
been determined crystallographically. an ‘inverted
inserts
(32) containing
have
ligands were found to form
of cis-[PtC12(PPh3)2]
gave the corresponding,
for example (33) whose structure was established
with (2,4,6air stable, cis-
using X-ray diffraction
1411.
(32)
cis-(34;
(33; R=‘Bu)
A convenient
one step method
for the synthesis
of dinuclear
R=CH,OH)
platinum(I1)
phosphine
complexes
has been reported. The procedure involves direct reaction of PtC12 and the appropriate
phosphine
in p-chlorotoluene
equivalents
to
[PtCl2(P(CHZOH)3]2]. [PtCl(P(CH20H)3]3]Cl, assigned
as
[42]. Addition of 3 equivalents
K2[PtC14]
results
gives, amongst
In
the
other things,
The new meso-ligand
of P(CH2OH)s of
the
to Na[PtCle] or 2
platinum(I1)
of P(CH20H)s
to this complex
presence
of
further
the bis(chelate)
gives
(34) [43]. The related phosphine
P(CHzOH)3,
salts trans-
and cis-
ligand Ph2PCH2OH
the structure of which has been
[44].
(R*,S*)-2,3-bis(diphenylphosphino)butane
(achiraphos)
and used to prepare the prochiral complex [PtC12(achiraphos)]. Displacement
the enantiotopic
complex
gives an unstable species tentatively
to give cis-[PtC12(Ph2PCHzOH)2],
determined by X-ray crystallography
synthesised
formation
while reaction with 2 equivalents
[Pt( (HOCH2)2PCH20P(CH20H)2)2]Clz with [PtClz(cod)]
the
Addition of a further equivalent
[PtCl(P(CH2OH)3)4]Cl.
[PtCl (P(CH2OH)3)4]Cl
reacted
in
chlorine atoms with [lR-(la,2P,5a)]-diphenylmenthylphosphine
has been of one of
(R-PMenPh2)
P. K. Byers/Coordination
440
and
subsequent
treatment
with
Chemistry Reviews
NH4PFe
gave
146 (I 995) 431-#50
diastereomeric
complexes
of the form
[PtCl(achiraphos)(R-PMenPh2)lPFe
(35). The solid state structure of one of the epimers has been
determined by X-ray crystallography
[45].
(35) Preparation
of the diphenyl(phenylethynyl)phosphine
For (36) intramolecular
coupling of the phosphinoacetylene
and from (37; X = Cl) the free unsymmetrical
diphosphine
complexes
(36) has been reported.
ligands occurs on heating to form (37), [o-Cl&Ito(PPh2)2],
generated by this
coupling step, has been isolated [46].
cl\
Ph
,:“‘=
c,/PtKIJh
E
Ph
2
(36) The series of complexes
(37) [PtXx’(r$(PPh2)$IH}]
(X = X’ = Cl, C&;
X = Cl, x’ = C&)
have been prepared, and 3tP( lH} NMR spectra indicate that one of the phosphorus triphosphine
ligand remains
N(Ph)PPhz
has been synthesised,
dimethylplatinum(II)
uncoordinated
[47]. The new diphosphine
and treatment
with [PtMez(cod)]
atoms of the
PPhZCH$JtBu)=Naffords
the expected
species (38) [48].
Ph2 “\pt/p\
R,P/*
YJN i’h,
tih (38) Treatment
(39) of cis-[PtC12(PR3)2]
with dppa {Ph2PN(H)PPh2)
(PR3 = PMe3, PMeTPh, PMePh2, P(nBu)g, PPh3, PEt3j
afforded the cationic complexes
[PtCl(PR3)(dppa)]Cl
(39), whilst
P.K. Byers/Coordimtion
reaction
of [PtC12(dppe)]
[PtCl(PMe2Ph)(dppa)]Cl,
with dppa gave [Pt(dppa)(dppe)]C12. [PtCl(P(nBu)3](dppa)]Cl
by X-ray crystallography phosphorus
and in each instance,
complexes
441
The molecular
and [Pt(dppa)(dppe)]Clz
structures
[PtC12{ RN[P(OPh)&]]
of
have been determined
reveal dppa acting as a chelate through
atoms [49]. The reaction of [PtC12(cod)] with RN[P(OPh)2]2
similar P,P’-chelate
both
(R = Me, Ph) affords
[50].
Complexes with nitrogen donor ligands
122.2
Reaction of organomercury complexes
ChemisrryReviews I46 (1995) 431&450
halides HgR’Cl (R’ = Me, Et, tBu, Ph) with the platinum(O)
[Pt(dmphen){ (Z)-RO$CH=CHC@R}]
(dmphen = 2,9-Me2-l,lO-phenanthroline;
R =
Me, Et, ~Bu) produced 5 coordinate platinum@) compounds of the form [PtCl(HgR’)(dmphen){
Q-
R02CCH=CHC02R)]
(40); the solid state structure of (40; R = Me, R’ = Me) was established
using X-ray diffraction
methods [Sl]. A second series of Scoordinate
general formula
[PtR(Cl)(N-N)(YC=CY)]
platinum@)
complexes
CH2Cl; R = Me, 4-MeOC&),
e.g. (41). have been prepared by treatment of [PtR(Cl)(N-N)]
alkynes.
alkyne:[PtMe(Cl)(dmphen)]
Using
a
1:2
[Pt2Me2(C1)2(YC=CY)(dmphen)]
ratio
were isolated, and for the but-2-yne
structure determined crystallographically
of
(N-N = didentate N-donor ligand; Y = CF3, COzMe,
dinuclear derivative
with
species the molecular
[52].
-/yCF3 / 3c
Cl
(40) Cyclometallation with platinum(I1) CH$eHg](lt-OAc)]2
reactions of N-benzyl and N-(phenylethyl)-cl-benzoylbenzylideneamines
salts have been reported, (42) established
2,9-diphenyl-l,lO-phenanthroline) (43) is substitution cyclometallated
(41)
and the structure
of [Pt{CeH4(CeH5C=O)C=N-
[53]. Reaction of [Pt(MeCN@+
gave the cyclometallated
labile, and can be replaced
with dpphen (dpphen =
complex (43). The acetonitrile ligand in
by nitrogen
derivative [PtLCl] (HL = &Bu-2,2’-bipyridine)
bases [54]. The synthesis has been reported [55].
0
0
L (42)
NCMe (43)
I
of the
P.K. Byers/Coordination
442
The mixed alkylplatinum(I1)
Chemistp
complex [Pt(CF3)(CH3)(nbd)]
(L2 = e.g. tmen, 2py, bpy) to afford the corresponding MeCN, [Pt(CF$(CH3)(MeCN)2]
Reviews 146 (1995) 431-450
complexes
reacts with neutral ligands L2 [Pt(CF3)(CH$(L2)],
whilst with
is formed in equilibrium with starting materials [56]. The kinetics
of CN- substitution at platinum@)
in the series cis- and trans.[PtC12(am)2]
(am = e.g. MezNH, py.
4-CNpy, 4-Clpy, 2-Mepy) has been investigated for the slow step in equation (i) [57]. [Pt(CN)2(am)2]
+ CN- +
Treatment of cis-[Pt(C&)2(thf)2]
(i)
with 2-benzyl pyridine gave cis-[Pt(C&)2(PhCH2py)]
(44), which in the solid state, as established platinum interaction.
[Pt(CN)3(am)]-
by X-ray diffraction,
exhibits
a weak $-benzyl
Subsequent reaction of (44) with CO yielded [Pt(C#s)2(PhCH2py-N)(CO)]
which did not contain a Pt-benzyl interaction [58].
E Q
xptyF” / C6F5
0
(44)
Three platinum(I1)
complexes
molecular structures determined
of l,l’-biisoquinoline
ligand was found to be didentate, whilst in the complexes biisoquinoline
adopted
[PtC13(NCR)]-
and cis- and truns-[PtClz(NCR)2]
and mixed amide-nitrile platinum. intermetallic
a unidentate
complexes,
The complexes interaction.
(biq) have been prepared and their
using X-ray crystallography.
bonding
mode
In one of these, [PtClz(biq)] (45) the
[Pt(biq)(L)3] (L = py, 4-NMe2py)
[59]. Mono-
(R = ~Bu, Me, Ph) hydrolyse
For example,
of two platinum(I1)
monomeric
cis-[PtC12( HN=C(OH)lBu)&
distance of 3.165(l) A [60].
(46)
l,l’-
complexes
to amidate-amide
with the amide ligands in the enol form and N-bound
are composed
(45)
and bis-nitrile
to
units, with a Pt-Pt
(46) possesses
a Pt-Pt
P.K. Byers/Coordination
Chemistry Reviews
Reaction of the complex [PtCl(@U!zH&tmen)]+ 3,6-his-(dimethylamino)acridine) molecule
by an ethylene
endocyclic
146 (1995)
443
431450
with acridines (3,6-diaminoacridine
and
afforded complexes in which the metal is linked to the polycyclic
chain. For 3,6-his-(dimethylamino)acridine
nitrogen to give (47) whilst for 3,6-diaminoacridine
attack occurred
at the
attack occurred at the exocyclic
aminic groups to afford (48); the structure of the former was established
using X-ray diffraction
[611. N
fr
(48”)
(47+)
Treatment
of cis- and trans-[PtC12(NCR)2]
tBu) with 2 equivalents
of [OCH2CH$l]-
rrans-[PtC12(N=C(R)OCH$ZH2)2] [Pt(terpy)L’]“+ spectroscopic
(R = 4-MePh, 4-CFsPh,
affords the bis(A2-1,3-oxazoline)
2-MePh, Et, nPr, jPr, derivatives
in high yield [62]. A series of platinum-terpy
cis- and
complexes
(L’ = Cl, Br, I, N3, SCN (n = 1); L’ = NH3 (n = 2)) have been prepared and their and emission
range of complexes
properties
studied [63]. The 1H NMR and vibrational
of the general formula [PtCl2(am)] (am = cycloalkylamine
spectra for a
CnH2,,_tNH2; n =
348) have been reported [64].
12.2.3
Complexes with sulfiir group donor ligands
The series isoquinoline-N-oxide,
of complexes
Z&se’s salt. Subsequent
reaction
afforded frans-[PtC12(L’)(4-MeQNO)] An account detailing tridentate
ligand
trans-[PtC12(C2Hq)L]
4-ClQNO, 2-MeQNO, 4-MeQNO)
(L = quinoline
N-oxide
(QNO),
have been prepared by addition of L to
of [PtC12(C2H4)(4_MeQNO)]
with L’ (L’ = CO, PPh3, py)
[65].
the synthesis
of a range of complexes
1,4,7-trithiacyclononane,
[9]aneSg
(49),
containing
has appeared.
the potentially The complexes
[PtRR’( [9]aneS3]] (R = R’= Me, Et, CH2CMe3, CHzSiMe3, Ph; R = Me, R’ = CH2SiMe3; R = Cl, R’= CHzSiMe3) were prepared by displacement [PtPh:!(]9]aneS3]1
of cod or nbd from appropriate precursors, and for
the molecular structure was established
by X-ray crystallography
[66]. In two
444
related
P.K. Byers/Coordi.mztion
reports,
the complexes
Chemistry Reviews 146 (1995) 431450
[Pt( (50))212+ [67] and [Pt((Sl)]]2+
[68] were prepared
and
structurally characterised using X-ray diffraction methods.
l-7
s-
rl
c,:,s_,9qj1 PlmeS3
[lOlaneS
(4%
[12]ane!&
(50)
The synthesis, characterisation,
X-ray structure determination
(51) and emission spectroscopy
of
(52) and (53) has been reported. Both complexes were obtained upon reaction of [PtCl;?(cod)] and the corresponding [Pt(&C)(py)]
dianionic
dithiolate
and [Pt($C)(PMe3)]
salt [69]. The platinum(II)
complexes
[Pt($C)]2,
(54) (S2C = 1,3-imidazolidinyl-N,W-hir(2-benzenethiolate)
have been prepared and fully characterised [70].
QNy+ S-pt-S
I
PMe, (54)
12.2.4
Complexes with mixed donor ligands
The new P,N-didentate prepare
the complexes
Ar)N(SiMe&)(PEt$l NJ-chelating spectroscopy
ligand (55), derived from valine, has been synthesised
[PtX2(55)]
(X = Cl, I) [71]. Reaction
(Ar = 4-MeCgHq) with PhSeCl was reported to give (56), containing
ligand PPhzN(H)C(Ar)=N(H). and X-ray crystallography
The structure of (56) was established
[72]. The dinuclear platinum compounds
have been isolated from the reaction of cis-[PtCl2(dmso)(PPh2py)] cis-[PtMg(dmso)2];
and used to
of trans-[PtCl2(PPhzNC(4the
using NMR (57) and (58)
with an equimolar quantity of
both complexes were the subject of an X-ray diffraction study [27].
P.K. Byers/Coordination
Chemistry Reviews 146 (1995) 431450
(56; Ar=4-MeC6H4)
Ph,P
Jo
Ph,P
i,Mei,“e s+
/
“t Pt-c
+
tc PPh2
c I--Pt-
I/‘t’ Cl
s
The ligands PhzPN(Ph)PPhz(=E) [PtClz(P-E)]
(E = S, Se) (P-E) have been used to prepare the mixed
(59), and for E = S the solid state structure has been established
[73]. The neutral, dimeric complexes
[(Pt(C&)(ttSPPh2)(PR3))2]
cationic complexe [Pt(SPPh2)(PPh+]C104
(PR3 = PPh3, PPh2Et) and
have been reported. For the former the [SPPh&
is present as a P,S-bridge whilst in the latter it adopts a P,S-chelating Treatment
of the chloro-bridged
the anion [C(PPh2)(P(S)Ph2)2](60) and [Pt(MeOcod)( isomers
complexes
of [PtClz(E-S)]
ligand
bonding mode [74].
[Pt$4(PEt&]
affords the complexes
C(PPh2)(P(S)Ph2)2-P,s)l,
[75]. The synthesis
complexes
I
(58)
(57; S=dmso)
donor complexes
/Jo
and [Pt2Clz(MeOcod)21
with
[PtCl(PEt3)(C(PPh2)(P(S)Ph2)2-P,S]] as a mixture of cis- and trans-
respectively,
(E-S = (+)Ph2ECHZCH$(O)Me
(E = P, As))
has been reported. In both cases, the ligand acts as an E,S-didentate
ligand, and M-O
bonds are not involved [76].
“\pt/S“/iph2
\pO’\
EtgPf
Ph2 (59) Reaction monomeric mono-anionic
of [Pt(C6F5)2(lt-C1)J22-
complex
[Pt(CtjFs)2(C5bNS)]-,
Fr2’
(60) with [CgHqNS]possessing
(pyridine-2-thiolate)
affords
the
a [N-S]- chelate. Upon reaction of this
complex with PPh3 the species [Pt(C&+(C5&NS)(PPh3)]-,
possessing
the ligand
446
P. K. Byers/Coordination
in a monodentate
S-binding
Chemistry Reviews 146 (1995) 431450
mode is obtained
[77]. The crystal structures
of four platinum(I1)
complex cations (61) containing the organic ligand 2,6-bis(methylthiomethyl)pyridine determined
by X-ray diffraction
NSPh] with [Pt(Q&)(PPh3)2]
have been
[78]. Reaction of rruns-[PhSNC(MeCeH4)N=NC(MeC6H& gave the platinum(II)
complex (62) in which the ligand is bonded
in a NjV’,S-tridentate fashion [79]
0
A 0
N
S-p*u-s+
I
X
(62; Ar=4-MeC,H,)
(61; X=CI, Br, SCN)
The thioether
and sulphinyl
azo-benzene
complexes
(63) and (64), respectively,
insert oxygen into the Pt-0 bond when treated with m-chloroperbenzoic containing the OJ,S-donor
slowly
acid to produce species
set [80].
o\ 0
Pt
N*
Nf
7
‘t
0
VR 0
o(63)
Treatment analogous
of platinum
palladium(U)
(64)
salts with L2- (65) affords
salt, [Pd2(L)12+,
macrocycle to be planar with inter-molecular
the complex
the solid state structure x-ring stacking [81].
(65)
[Pt2(L)12’.
showed
For the
the dinucleating
P.K. Byers/Coordinution
12.3
447
Chemistry Reviews 146 (1995) 431ASO
PLATINUM(I)
The first example of a p-parallel ligated phospha-alkyne [Pt2Cl&-dppm)2Q.t-IBUCP)] NMR spectroscopy
has been reported for the complex
(66). The structure of the molecule was elucidated by 3lP and 195Pt
[82].
‘“.9/‘\r
PPh2
p-c
c I-y-
I
t
pI Ph2pvPPh2 (66;
Reaction of [Pt$&(dppm)2] afforded the new compounds
R=‘Bu)
with 2 L (L = quinoline, N-methylimidazole,
gave [Pt2(dppm)2(L’)Cl]+. For (67; L = quinoline, N-methylimidazole) solid state structure
4-lbutylpyridine)
[Pt2(dppm)2L212+ (67), whilst reaction with L’ = 2,4,6-Me3pyridine
was determined
crystallographically,
2.615(l), 2.580(l) and 2.627(2) A, respectively,
and [Pt2(dppm)&‘)Cl]+
and the Pt-Pt distances
the
found to be
thus establishing the presence of a Pt-Pt bond [83].
L*Pt-Pt-L
L=
t
t ‘B u
Ph2pVPPh2 (67”)
12.4
PLATINUM(O)
Reaction of 1-bromocycloheptene tBuOK in the presence of [Pt(PPh&] of the corresponding thf in the presence
or a mixture of l-, 2- and 3-bromocycloheptamenes
led to the predominant
formation of Pt(PPh$z
with
A-complexes
cyclic allenes, e.g. (68). In contrast, reaction of the same halides with LDA in of [Pt(PPhg)g]
gave exclusively
Pt(PPh3)2 complexes
of the corresponding
cyclic alkynes, e.g. (69) [84]. The preparation (C02Et)=CH(C02Et)
of [Pt(trans-CH(COzEt)=CH(CO2Et)}(PPh3)2]
and [Pt(cis-CH-
1(PPh3)2] has been described. The complexes were prepared by reaction of
]Pt(q2-CH2CH$(PPh3)2]
with frans- and cisCH(C02Et)=CH(C02Et),
[Pt(rruns-CH(C02Et)=CH(CO2Et)](PPh3)2]
the structure was determined
1851. The platinum(O) dimer [Pt&-CO)(CO)2Q.t-dppm)2]
respectively,
and for
from an X-ray analysis
(70) has been prepared from [Pt$12(p-
P. K. Byers/Coordimtion
448
dppm)2] via NaBH4 reduction [Pt2(p-dppm)3]
Chemistry Reviews 146 (1995) 431450
under a CO atmosphere
and by substitution
of a dppm ligand in
with CO [ 861.
d”““”
o+Pt(PPh3J2
ph;zk$p;h2 2
(68)
(69)
2
(70)
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