TY - JOUR
T1 - Tertiary phosphine adducts of manganese(II) dialkyls. Part 2. Synthesis, properties, and structures of monomeric complexes
AU - Howard, Christopher G.
AU - Girolami, Gregory S.
AU - Wilkinson, Geoffrey
AU - Thornton-Pett, Mark
AU - Hursthouse, Michael B.
N1 - Funding Information:
CzoH40MnP4, M = 460.35,Monoclinic, a = 9.153(8), b = 16.001(2), c = 17.282(4) A,p = 103.66(3)", U = 2459.5 A3, space group P24a (equiva-lent to P21/c, no. 14) Z = 4, D, = 1.24 g ~ m - ~ , p(Mo-K,) =6.16 cm-I, T = 295 K.Data collection. Parameters as above; 4 314 unique data,3 177 observed.Structure refinement. Number of parameters = 380, weight-ing factor g = 0.0007, R = 0.047, R' = 0.049.Lists of final atomic co-ordinates for compounds (1) and (6)are given in Tables 7 and 8 respectively.AcknowledgementsWe are greatly indebted to Dr. J. F. Gibson and Dr. P. Beard-wood for their help and advice. We also thank the S.E.R.C.for the purchase of the diffractometer and the National ScienceFoundation (U.S.) for a N.A.T.O. Postdoctoral Fellowship(to G. S. G.).References1 Part 1, C. G. Howard, G. Wilkinson, M. Thornton-Pett, andM. B. Hursthouse, J. Chem. SOC., Dalton Trans., 1983, 2025.2 R. A. Andersen, E. Carmona-Guzman, J. F. Gibson, and G.Wilkinson, J. Chem. SOC., Dalton Trans., 1976, 2204.3 K. Jacob and K-H. Thiele, 2. Anorg. Allg. Chem., 1979, 455,3.4 D. C. Bradley, J. D. J. Backer-Dirks, M. B. Hursthouse, K. M. A.Malik, and R. Moseler, unpublished work.5 M. F. Lappert, T. R. Martin, C. L. Raston, B. W. Skelton, andA. H. White, J. Chem. SOC., Dalton Trans., 1982, 1959.6 S. D. Chappell, D. J. Cole-Hamilton, A. M. R. Galas, and M. B.Hursthouse, J. Chem. SOC., Dalton Trans., 1982, 1867 and refs.therein.7 R. D. Dowsing and J. F. Gibson, J. Chem. Phys., 1969, 50,294.8 H. H. Wickman, M. P. Klein, and D. A. Shirley, J. Chem. Phys.,1965,42,2113.9 D. Vivien and J. F. Gibson, J. Chem. SOC., Faraday Trans. 2,1975, 1640.10 C. A. Kosky, J-P. Gayda, J. F. Gibson, S. F. Jones, and D. J.Williams, Inorg. Chem., 1982, 21, 3173.1 1 H. Venoyama and K. Sakai, Spectrochim. Acta, Part A , 1975,31, 1517.12 R. D. Dowsing, J. F. Gibson, D. M. L. Goodgame, M. Good-game, and P. J. Hayward, J. Chem. SOC. A , 1969, 1242.13 R. L. Harlow, P. J. Krusic, R. J. McKinney, and S. S. Wreford,Organometallics, 1982, 1, 1506.14 P. B. Hitchcock, M. F. Lappert, and C. R. C. Milne, J . Chem.Sac., Dalton Trans., 1981, 180 and refs. therein.15 C. G. Howard, G . S. Girolami, G. Wilkinson, M. Thornton-Pett, and M. B. Hursthouse, J. Chem. SOC., Chern. Contmun.,1983, 1163.16 See, for example, T. H. Tulip and D. L. Thorn, J. Am. Chem.Soc., 1981, 103, 2448.17 D. F. Evans, G . V. Fazakerley, and R. F. Phillips, J. Chem. SOC.A, 1971, 1931.18 R. A. Andersen and G. Wilkinson, J. Chem. Soc., Dalton Trans.,1977, 809.19 M. B. Hursthouse, R. A. Jones, K. M. A. Malik, and G.Wilkinson, J. Am. Chom. SOC., 1979, 101, 4128.Received 30th March 1983; Paper 3/51
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Copyright 2015 Elsevier B.V., All rights reserved.
PY - 1983
Y1 - 1983
N2 - Monomeric tetrahedral manganese dialkyl tertiary phosphine complexes of stoicheiometry MnR2(PR′3)2 have been identified in solutions by electron spin resonance spectra and the alkyl complex Mn(CH2CMe2Ph)2(PMe3)2 isolated and structurally characterised by X-ray crystallography. The molecule has a severely distorted tetrahedral geometry with P-Mn-P and C-Mn-C angles of 96.2 and 137.9° respectively, which reflect the relative sizes of the two kinds of ligand. The Mn-C and Mn-P distances are 2.149(6) and 2.633(4) Å respectively. Use of the chelating phosphine, 1,2-bis(dimethylphosphino)ethane (dmpe), has allowed the isolation of the tetrahedral monomers MnR2(dmpe) (R = CH2SiMe3, CH2CMe3, and CH2Ph). The chelate dialkyl o-xylylene, o-(CH2)2C6H4, gives an octahedral complex Mn[o-(CH2)2C6H4](dmpe)2 whose structure has also been determined by X-ray diffraction. In this molecule, all metal-ligand bond lengths are shorter than the corresponding bonds in Mn(CH2CMe2Ph)2(PMe3)2. This is consistent with a significant reduction in the MnII radius on adoption of the low-spin state observed. The Mn-C distances are 2.110(5) and 2.1 04(6) Å, while the Mn-P distances of 2.230(3) (trans to P) and 2.298(3) Å (trans to C) reflect the different trans-influence abilities of alkyls and phosphines. The X-band e.s.r. spectra of the monomeric complexes have been studied in detail and are discussed in terms of distorted tetrahedral high-spin MnII and octahedral low-spin MnII species.
AB - Monomeric tetrahedral manganese dialkyl tertiary phosphine complexes of stoicheiometry MnR2(PR′3)2 have been identified in solutions by electron spin resonance spectra and the alkyl complex Mn(CH2CMe2Ph)2(PMe3)2 isolated and structurally characterised by X-ray crystallography. The molecule has a severely distorted tetrahedral geometry with P-Mn-P and C-Mn-C angles of 96.2 and 137.9° respectively, which reflect the relative sizes of the two kinds of ligand. The Mn-C and Mn-P distances are 2.149(6) and 2.633(4) Å respectively. Use of the chelating phosphine, 1,2-bis(dimethylphosphino)ethane (dmpe), has allowed the isolation of the tetrahedral monomers MnR2(dmpe) (R = CH2SiMe3, CH2CMe3, and CH2Ph). The chelate dialkyl o-xylylene, o-(CH2)2C6H4, gives an octahedral complex Mn[o-(CH2)2C6H4](dmpe)2 whose structure has also been determined by X-ray diffraction. In this molecule, all metal-ligand bond lengths are shorter than the corresponding bonds in Mn(CH2CMe2Ph)2(PMe3)2. This is consistent with a significant reduction in the MnII radius on adoption of the low-spin state observed. The Mn-C distances are 2.110(5) and 2.1 04(6) Å, while the Mn-P distances of 2.230(3) (trans to P) and 2.298(3) Å (trans to C) reflect the different trans-influence abilities of alkyls and phosphines. The X-band e.s.r. spectra of the monomeric complexes have been studied in detail and are discussed in terms of distorted tetrahedral high-spin MnII and octahedral low-spin MnII species.
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U2 - 10.1039/DT9830002631
DO - 10.1039/DT9830002631
M3 - Article
AN - SCOPUS:37049097012
SN - 1472-7773
SP - 2631
EP - 2637
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 12
ER -