On the Nature of the Bonding in Metal-Silane sigma-Complexes

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dc.creatorMcGrady, G. Sean
dc.creatorSirsch, Peter
dc.creatorChatterton, Nicholas P.
dc.creatorOstermann, Andreas
dc.creatorGatti, Carlo
dc.creatorAltmannshofer, Sandra
dc.creatorHerz, Verena
dc.creatorEickerling, Georg
dc.creatorScherer, Wolfgang
dc.date2008-11-04
dc.date.accessioned2026-07-07T10:15:22Z
dc.date.available2026-07-07T10:15:22Z
dc.descriptionThe nature of metal silane sigma-bond interaction has been investigated in several key systems by a range of experimental and computational techniques. The structure of [Cp'Mn(CO)2(eta2-HSiHPh2)] 1 has been determined by single crystal neutron diffraction, and the geometry at the Si atom is shown to approximate to a trigonal bipyramid. This complex is similar to [Cp'Mn(CO)2(eta2-HSiFPh2)] 2, whose structure and bonding characteristics have recently been determined by charge density studies based on high-resolution X-ray and neutron diffraction data. The geometry at the Si atom in these sigma-bond complexes is compared with that in other systems containing hypercoordinate silicon. The Mn-H distances for 1 and 2 in solution have been estimated using NMR T1 relaxation measurements, giving a value of 1.56(3) AA in each case, in excellent agreement with the distances deduced from neutron diffraction. DFT calculations have been employed to explore the bonding in the Mn-H-Si unit in 1 and 2 and in the related system [Cp'Mn(CO)2(eta2-HSiCl3)] 3. These studies support the idea that the oxidative addition of a silane ligand to a transition metal center may be described as an asymmetric process in which the Mn-H bond is formed at an early stage, while both the establishment of the Mn-Si bond and also the activation of the eta2-coordinated Si-H moiety are controlled by the extent of Mn-> sigma*(X-Si-H) back-donation, which increases with increasing electronwithdrawing character of the X substituent trans to the metal-coordinated Si-H bond. This delocalized molecular orbital (MO) approach is complemented and supported by combined experimental and theoretical charge density studies including the source function S(r,Omega).
dc.description39 pages, 7 figures, 4 tables
dc.identifierhttps://arxiv.org/abs/0811.0451
dc.identifierhttp://arxiv.org/abs/0811.0451
dc.identifier.urihttp://salesiana.dossiersoluciones.com/handle/123456789/173150
dc.subjectChemical Physics
dc.titleOn the Nature of the Bonding in Metal-Silane sigma-Complexes
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