Journal of the Chemical Society, Dalton Transactions p. 2235 - 2244 (1981)
Update date:2022-08-04
Topics:
Benson, Ian B.
Knox, Selby A. R.
Naish, Pamela J.
Welch, Alan J.
Thiolato-bridged dimolybdenum complexes a low-energy sulphur inversion process, such that complete averaging of R group environments is achieved on the n.m.r. time scale.Interconverting isomers are also present for the monosubstituted derivatives a limited averaging is observed, generating a time-averaged mirror plane of molecular symmetry.This results from the presence of a phosphorus ligand trans to one bridging sulphur and of CO trans to the other two, shown in an X-ray diffraction study of a=10.186(7), b=15.677(7), c=19.821(15) Angstroem, and β=96.31(5) deg.The structure has been solved by conventional techniques and refined by least to R 0.046 for 5149 diffractometer-measured reflection intensities.Three bridging SBut groups display an asymmetric stereochemistry about a Mo-Mo bond <2.9460(15) Angstroem>, rationalised on the basis of intramolecular terminal ligand-bridging ligand contacts.One molybdenum is η7 co-ordinated to a cycloheptatrienyl ring while the other carries the two CO groups and a P(OMe)3 ligand.Metal-sulphur distances range over 2.411(2)-2.549(2) Angstroem and Mo-P is 2.445(2) Angstroem.Free energies of activation for sulphur inversion as low as 46 kJmol-1 have been derived from coalescence temperatures for several complexes.
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