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Reactions and crystal structures of heterodinuclear complexes R3Sn–M(CO)5 (M = Mn, Re) with some nitrogen ligands
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Chinese Chemical Letters 20 (2009) 465–468 www.elsevier.com/locate/cclet
Reactions and crystal structures of heterodinuclear complexes R3Sn–M(CO)5 (M = Mn, Re) with some nitrogen ligands Yong Qiang Ma a,b,*, Ning Yin b, Wen Jing Peng b, Jing Li b,** a
b
Department of Applied Chemistry, China Agriculture University, Beijing 100193, China State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China Received 8 September 2008
Abstract Some reactions of R3SnM(CO)5 (M = Mn, Re) with CH3CN or pyridine were investigated to give complexes R3SnMn(CO)3LL0 or R3SnMn(CO)4L by a facile mild method. X-ray diffractions analyses show that, in contrast to the phosphine ligand occupying in axial position, nitrogen ligands occupy equatorial position. # 2008 Yong Qiang Ma. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved. Keywords: Reactions; Heterodinuclear complexes; X-ray structure
Heterodinuclear complexes with a direct polar metal–metal bond (Sn–M) have been a subject of interest in the recent years because of their interesting structural and reactive features as well as potential catalytic activity possibly for the sake of the cooperation effects of two metals [1–4]. Although a number of these compounds have been synthesized, the study of reactions about these covalent bimetallic complexes is still very limited relatively. The only monosubstitute complexes Ph3SnMn(CO)4PPh3, was synthesized by R.D. Gorsicd [5] from the reaction of Ph3SnMn(CO)5 with excess PPh3 at about 200 8C in the absence of solvent or from Ph3SnCl and NaMn(CO)4PPh3. In this work, we present a novel mild method to mono- and disubstitute the transition–metal complexes with some nitrogen ligands. We also found nitrogen ligands occupy equatorial position by X-ray crystal analysis. 1. Experimental All manipulations were carried out under an argon atmosphere with the use of standard Schlenk and high vacuum line techniques. Solvents were distilled from conventional drying agents and degassed prior to use. Me3 NO2H2 O
R3 SnMðCOÞ5 þ L
!
R3 SnMðCOÞnðLÞ5 n n ¼ 1; 2
Ph3SnMn(CO)3(CH3CN)2(1), typically, to Ph3SnMn(CO)5 0.2 mmol in CH3CN 20 mL Me3NO2H2O 0.066 mg, 0.6 mmol was added. The mixture was stirred for 1 h and filtered. The filtrate was evaporated in vacuo. The obtained * Corresponding author at: Department of Applied Chemistry, China Agriculture University, Beijing 100193, China. ** Corresponding author. E-mail addresses: [email protected] (Y.Q. Ma), [email protected] (J. Li). 1001-8417/$ – see front matter # 2008 Yong Qiang Ma. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved. doi:10.1016/j.cclet.2008.12.017
466
Y.Q. Ma et al. / Chinese Chemical Letters 20 (2009) 465–468
solid was recrystallized from CH3CN. Yield: 65%. Elemental analysis found (calcd.) (%) C 52.69(52.58), H 3.83(3.71), N 4.90(4.91). Important infrared data [THF, y(CO) cm1]: 1995, 1991.0, 1879.4. 1H NMR (CDCl3, d ppm): 7.25–7.62(m, 15H, C6H5); 1.94(s, 3H, CH3). Ph3SnRe(CO)3(CH3CN)2(2), yield: 40%. Elemental analysis found (calcd.)(%) C 43.13(42.75), H 3.02(3.01), N 3.90(3.99). Important infrared data [THF, y(CO) cm1]: 2006.8, 1991.0, 1881.0. 1H NMR (CDCl3, d ppm): 7.23– 7.55(m, 15H, C6H5); 2.05(s, 6H, CH3). Cy3SnMn(CO)4(CH3CN)(3), yield: 80%. Elemental analysis found (calcd.)(%) C 50.13(50.03), H 6.27(6.30), N 2.76(2.43). Important infrared data [THF, y(CO) cm1]: 2037, 1965, 1938, 1967. 1H NMR (CDCl3, d ppm): 2.14(s, 3H, CH3); 1.21–1.90(m, 33H, C6H11). 13C NMR (d ppm): 222.9[s(br), Mn–CO], 130.77[s, Mn–NC], 32.90–27.43[m, C of C6H11], 4.330 [s, CH3]. 119Sn NMR d 30.73(s). Cy3SnMn(CO)4(C5H5N)(4), yield: 55%. Elemental analysis found (calcd.)(%) C 52.41 (52.80), H 6.49 (6.24), N 2.5 8(2.28). Important infrared data [THF, y(CO) cm1]: 2028, 1921. 1H NMR (CDCl3, d ppm): 7.12–6.59(m, 5H, C5H5N); 1.19–1.61 (33H, C6H11). 13C NMR (d ppm) 222.9[s(br), Mn–CO], 156.75, 136.79, 124.67[m, C5H5N], 32.84–27.27[m, C of C6H11]. X-ray crystallography Diffraction data for compound 2, 4 were obtained on a Bruker Smart 1000 CCD or Enraf-nonius CAD4 ˚ ). Unit cell dimensions were obtained with least squares diffractometer (Mo-Ka radiation, l = 0.71073 A refinements and the structure was solved by direct methods using SHELX-97 program [5]. All data were corrected using SADABS method. The important crystal data were as follows: complex 2: C25H21N2O3ReSn, Fw = 702, ˚ , b = 10.141(2) A ˚ , c = 17.254(4); monoclinic, D(cal.) = 1.864 mg/m3, space group P2(1)/n, a = 17.454(4) A 1 b = 113.57(3)8; Z = 4, m = 1.858 mm , R(uniq) = 2211, R1 = 0.0368, wR2 = 0.0960 [I > 2s(I)]. Complex 4: ˚, C27H38MnNO4Sn, Fw = 614, orthorhombic, D(cal.) = 1.453 mg/m3, space group Pna2(1), a = 13.364(3) A 1 ˚ ˚ b = 12.242(2) A, c = 15.296(3) A, b = 908; Z = 4, m = 1.373 mm , R(uniq) = 5320, R1 = 0.0337, wR2 = 0.0870 [I > 2s(I)]. 2. Results and discussion Carbon monoxide of R3SnMn(CO)5 can be displaced from metal carbonyls with varying difficulty by compounds such as triphenylphosphine either thermally or catalytically (ultraviolet) in Ref. [6]. In this paper, a facile mild method for synthesis of the mono- or disubstitute heterodinuclear carbonyl complexes R3SnM(CO)4L or R3SnM(CO)3L2
Fig. 1. Molecular structure of 2.
Y.Q. Ma et al. / Chinese Chemical Letters 20 (2009) 465–468
467
Fig. 2. Molecular structure of 4.
(L = CH3CN, C5H5N) was made possible by amine oxide promotion instead of by the reported synthesis [5] which involves high temperature. The reaction of Cy3SnMn(CO)5 with CH3CN or pyridine in the presence of Me3NO2H2O was found to yield the monosubstitute derivative Cy3SnMn(CO)4(L) in good yield; under the similar conditions for Ph3SnMn(CO)5 disubstitute derivatives Ph3SnMn(CO)3L2 were obtained, when L = CH3CN, C5H5N. Suitable crystals (2, 4) were obtained in ethyl ether/hexane or CH2Cl2/CH3OH at 20 8C. The molecular structures of 2, 4 are depicted in Figs. 1 and 2. Crystal structure Ph3SnRe(CO)3(CH3CN)2. The stereochemistry of tin is typically tetrahedral geometry. The ˚ ] is slightly longer than the corresponding bond in Ph3SnRe(CO)5 metal–metal bond Sn–Re [Sn(1)–Re(1), 2.755(11) A ˚ [Re–Sn (2.740 A)] [5]. Both CH3CN ligands occupy the neighboring equatorial positions. The Re–N distances are ˚ , respectively. The coordination geometry of Re can be described as a distorted octahedral 2.112(13) and 2.172(13) A with the plane being defined by two nitrogen from CH3CN and two carbon atoms from CO while the other CO and the ˚. Sn of SnPh3 occupying the axial positions. The five atoms N(1), N(2), C(1), C(2), Re(1) are coplanar within 0.0321 A ˚ The Re atom is displaced by 0.0802 A towards C(1) from the plane described by the equatorial N(1), N(2), C(1) and C(2). The axial C(3)–Re(1)–Sn(1) angle is 176.28. Crystal structure of Cy3SnMn(CO)4(C5H5N). The overall geometry of the molecule 4 is similar to that found for Ph3SnRe(CO)3(CH3CN)2 with the tin atom tetrahedral co-ordinate, the manganese atom octahedrally. The C5H5N occupy the equatorial position whereas the PPh3 ligand occupying the axial position in the monosubstitute analog Ph3SnMn(CO)4PPh3 [7]. As expected due to the difference of the atomic radii of Mn and Re, the bond Mn(2)–N(11) ˚ ) in 4 is shorter than the corresponding distance Re–N (2.112(13), 2.172(13) A ˚ ) in 2. The five atoms N(1), (2.106(4) A ˚ C(1), C(2), C(3) Mn(1) is coplanar with the mean deviation 0.0954 A. The metal–metal bond length [Sn(1)–Mn(2) ˚ ] is longer than the corresponding values of Ph3SnMn(CO)5 [2.674(4) A ˚ ], Me3SnMn(CO)5 [2.674(4) A ˚ ] [8] 2.7139 A ˚ and Ph3SnMn(CO)4PPh3 [2.627(10) A]. Acknowledgment This work was supported by the National Natural Science Foundation of China (No. 29672018). References [1] [2] [3] [4]
N. Wheatley, P. Kalck, Chem. Rev. 99 (1999) 3379. L.F. Tang, J.F. Chai, S.B. Zhao, J.T. Wang, J. Organomet. Chem. 669 (2003) 57. I. Saur, G. Rima, K. Miqueu, H. Gornitzka, J. Barrau, J. Organomet. Chem. 672 (2003) 77. R.H. Heyn, T.D. Tilley, J. Am. Chem. Soc. 114 (1992) 1917.
468 [5] [6] [7] [8]
Y.Q. Ma et al. / Chinese Chemical Letters 20 (2009) 465–468 R.D. Gorsich, J. Am. Chem. Soc. 84 (1962) 2486. G.M. Sheldrick, SHELXS-97, in: Program for X-ray Crystal Structure Solution, Gottingen University, Germany, 1997. D. Christendat, I. Wharf, A.M. Lebuis, I.S. Butler, D.F.R. Gilson, Inorg. Chim. Acta 329 (2002) 36. C. Loubser, J.L.M. Dillen, S. Lotz, Polyhedron 10 (1991) 2535.
Chinese Chemical Letters 20 (2009) 465–468 www.elsevier.com/locate/cclet
Reactions and crystal structures of heterodinuclear complexes R3Sn–M(CO)5 (M = Mn, Re) with some nitrogen ligands Yong Qiang Ma a,b,*, Ning Yin b, Wen Jing Peng b, Jing Li b,** a
b
Department of Applied Chemistry, China Agriculture University, Beijing 100193, China State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China Received 8 September 2008
Abstract Some reactions of R3SnM(CO)5 (M = Mn, Re) with CH3CN or pyridine were investigated to give complexes R3SnMn(CO)3LL0 or R3SnMn(CO)4L by a facile mild method. X-ray diffractions analyses show that, in contrast to the phosphine ligand occupying in axial position, nitrogen ligands occupy equatorial position. # 2008 Yong Qiang Ma. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved. Keywords: Reactions; Heterodinuclear complexes; X-ray structure
Heterodinuclear complexes with a direct polar metal–metal bond (Sn–M) have been a subject of interest in the recent years because of their interesting structural and reactive features as well as potential catalytic activity possibly for the sake of the cooperation effects of two metals [1–4]. Although a number of these compounds have been synthesized, the study of reactions about these covalent bimetallic complexes is still very limited relatively. The only monosubstitute complexes Ph3SnMn(CO)4PPh3, was synthesized by R.D. Gorsicd [5] from the reaction of Ph3SnMn(CO)5 with excess PPh3 at about 200 8C in the absence of solvent or from Ph3SnCl and NaMn(CO)4PPh3. In this work, we present a novel mild method to mono- and disubstitute the transition–metal complexes with some nitrogen ligands. We also found nitrogen ligands occupy equatorial position by X-ray crystal analysis. 1. Experimental All manipulations were carried out under an argon atmosphere with the use of standard Schlenk and high vacuum line techniques. Solvents were distilled from conventional drying agents and degassed prior to use. Me3 NO2H2 O
R3 SnMðCOÞ5 þ L
!
R3 SnMðCOÞnðLÞ5 n n ¼ 1; 2
Ph3SnMn(CO)3(CH3CN)2(1), typically, to Ph3SnMn(CO)5 0.2 mmol in CH3CN 20 mL Me3NO2H2O 0.066 mg, 0.6 mmol was added. The mixture was stirred for 1 h and filtered. The filtrate was evaporated in vacuo. The obtained * Corresponding author at: Department of Applied Chemistry, China Agriculture University, Beijing 100193, China. ** Corresponding author. E-mail addresses: [email protected] (Y.Q. Ma), [email protected] (J. Li). 1001-8417/$ – see front matter # 2008 Yong Qiang Ma. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved. doi:10.1016/j.cclet.2008.12.017
466
Y.Q. Ma et al. / Chinese Chemical Letters 20 (2009) 465–468
solid was recrystallized from CH3CN. Yield: 65%. Elemental analysis found (calcd.) (%) C 52.69(52.58), H 3.83(3.71), N 4.90(4.91). Important infrared data [THF, y(CO) cm1]: 1995, 1991.0, 1879.4. 1H NMR (CDCl3, d ppm): 7.25–7.62(m, 15H, C6H5); 1.94(s, 3H, CH3). Ph3SnRe(CO)3(CH3CN)2(2), yield: 40%. Elemental analysis found (calcd.)(%) C 43.13(42.75), H 3.02(3.01), N 3.90(3.99). Important infrared data [THF, y(CO) cm1]: 2006.8, 1991.0, 1881.0. 1H NMR (CDCl3, d ppm): 7.23– 7.55(m, 15H, C6H5); 2.05(s, 6H, CH3). Cy3SnMn(CO)4(CH3CN)(3), yield: 80%. Elemental analysis found (calcd.)(%) C 50.13(50.03), H 6.27(6.30), N 2.76(2.43). Important infrared data [THF, y(CO) cm1]: 2037, 1965, 1938, 1967. 1H NMR (CDCl3, d ppm): 2.14(s, 3H, CH3); 1.21–1.90(m, 33H, C6H11). 13C NMR (d ppm): 222.9[s(br), Mn–CO], 130.77[s, Mn–NC], 32.90–27.43[m, C of C6H11], 4.330 [s, CH3]. 119Sn NMR d 30.73(s). Cy3SnMn(CO)4(C5H5N)(4), yield: 55%. Elemental analysis found (calcd.)(%) C 52.41 (52.80), H 6.49 (6.24), N 2.5 8(2.28). Important infrared data [THF, y(CO) cm1]: 2028, 1921. 1H NMR (CDCl3, d ppm): 7.12–6.59(m, 5H, C5H5N); 1.19–1.61 (33H, C6H11). 13C NMR (d ppm) 222.9[s(br), Mn–CO], 156.75, 136.79, 124.67[m, C5H5N], 32.84–27.27[m, C of C6H11]. X-ray crystallography Diffraction data for compound 2, 4 were obtained on a Bruker Smart 1000 CCD or Enraf-nonius CAD4 ˚ ). Unit cell dimensions were obtained with least squares diffractometer (Mo-Ka radiation, l = 0.71073 A refinements and the structure was solved by direct methods using SHELX-97 program [5]. All data were corrected using SADABS method. The important crystal data were as follows: complex 2: C25H21N2O3ReSn, Fw = 702, ˚ , b = 10.141(2) A ˚ , c = 17.254(4); monoclinic, D(cal.) = 1.864 mg/m3, space group P2(1)/n, a = 17.454(4) A 1 b = 113.57(3)8; Z = 4, m = 1.858 mm , R(uniq) = 2211, R1 = 0.0368, wR2 = 0.0960 [I > 2s(I)]. Complex 4: ˚, C27H38MnNO4Sn, Fw = 614, orthorhombic, D(cal.) = 1.453 mg/m3, space group Pna2(1), a = 13.364(3) A 1 ˚ ˚ b = 12.242(2) A, c = 15.296(3) A, b = 908; Z = 4, m = 1.373 mm , R(uniq) = 5320, R1 = 0.0337, wR2 = 0.0870 [I > 2s(I)]. 2. Results and discussion Carbon monoxide of R3SnMn(CO)5 can be displaced from metal carbonyls with varying difficulty by compounds such as triphenylphosphine either thermally or catalytically (ultraviolet) in Ref. [6]. In this paper, a facile mild method for synthesis of the mono- or disubstitute heterodinuclear carbonyl complexes R3SnM(CO)4L or R3SnM(CO)3L2
Fig. 1. Molecular structure of 2.
Y.Q. Ma et al. / Chinese Chemical Letters 20 (2009) 465–468
467
Fig. 2. Molecular structure of 4.
(L = CH3CN, C5H5N) was made possible by amine oxide promotion instead of by the reported synthesis [5] which involves high temperature. The reaction of Cy3SnMn(CO)5 with CH3CN or pyridine in the presence of Me3NO2H2O was found to yield the monosubstitute derivative Cy3SnMn(CO)4(L) in good yield; under the similar conditions for Ph3SnMn(CO)5 disubstitute derivatives Ph3SnMn(CO)3L2 were obtained, when L = CH3CN, C5H5N. Suitable crystals (2, 4) were obtained in ethyl ether/hexane or CH2Cl2/CH3OH at 20 8C. The molecular structures of 2, 4 are depicted in Figs. 1 and 2. Crystal structure Ph3SnRe(CO)3(CH3CN)2. The stereochemistry of tin is typically tetrahedral geometry. The ˚ ] is slightly longer than the corresponding bond in Ph3SnRe(CO)5 metal–metal bond Sn–Re [Sn(1)–Re(1), 2.755(11) A ˚ [Re–Sn (2.740 A)] [5]. Both CH3CN ligands occupy the neighboring equatorial positions. The Re–N distances are ˚ , respectively. The coordination geometry of Re can be described as a distorted octahedral 2.112(13) and 2.172(13) A with the plane being defined by two nitrogen from CH3CN and two carbon atoms from CO while the other CO and the ˚. Sn of SnPh3 occupying the axial positions. The five atoms N(1), N(2), C(1), C(2), Re(1) are coplanar within 0.0321 A ˚ The Re atom is displaced by 0.0802 A towards C(1) from the plane described by the equatorial N(1), N(2), C(1) and C(2). The axial C(3)–Re(1)–Sn(1) angle is 176.28. Crystal structure of Cy3SnMn(CO)4(C5H5N). The overall geometry of the molecule 4 is similar to that found for Ph3SnRe(CO)3(CH3CN)2 with the tin atom tetrahedral co-ordinate, the manganese atom octahedrally. The C5H5N occupy the equatorial position whereas the PPh3 ligand occupying the axial position in the monosubstitute analog Ph3SnMn(CO)4PPh3 [7]. As expected due to the difference of the atomic radii of Mn and Re, the bond Mn(2)–N(11) ˚ ) in 4 is shorter than the corresponding distance Re–N (2.112(13), 2.172(13) A ˚ ) in 2. The five atoms N(1), (2.106(4) A ˚ C(1), C(2), C(3) Mn(1) is coplanar with the mean deviation 0.0954 A. The metal–metal bond length [Sn(1)–Mn(2) ˚ ] is longer than the corresponding values of Ph3SnMn(CO)5 [2.674(4) A ˚ ], Me3SnMn(CO)5 [2.674(4) A ˚ ] [8] 2.7139 A ˚ and Ph3SnMn(CO)4PPh3 [2.627(10) A]. Acknowledgment This work was supported by the National Natural Science Foundation of China (No. 29672018). References [1] [2] [3] [4]
N. Wheatley, P. Kalck, Chem. Rev. 99 (1999) 3379. L.F. Tang, J.F. Chai, S.B. Zhao, J.T. Wang, J. Organomet. Chem. 669 (2003) 57. I. Saur, G. Rima, K. Miqueu, H. Gornitzka, J. Barrau, J. Organomet. Chem. 672 (2003) 77. R.H. Heyn, T.D. Tilley, J. Am. Chem. Soc. 114 (1992) 1917.
468 [5] [6] [7] [8]
Y.Q. Ma et al. / Chinese Chemical Letters 20 (2009) 465–468 R.D. Gorsich, J. Am. Chem. Soc. 84 (1962) 2486. G.M. Sheldrick, SHELXS-97, in: Program for X-ray Crystal Structure Solution, Gottingen University, Germany, 1997. D. Christendat, I. Wharf, A.M. Lebuis, I.S. Butler, D.F.R. Gilson, Inorg. Chim. Acta 329 (2002) 36. C. Loubser, J.L.M. Dillen, S. Lotz, Polyhedron 10 (1991) 2535.