http://www.cnr.it/ontology/cnr/individuo/prodotto/ID48252

Nature of the Bonding in Metal-Silane sigma-Complexes (Articolo in rivista)

Type

Articolo in rivista (Classe)
Prodotto della ricerca (Classe)

Label

Nature of the Bonding in Metal-Silane sigma-Complexes (Articolo in rivista) (literal)

Anno

2009-01-01T00:00:00+01:00 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi

10.1021/ic8019777 (literal)

Alternative label

McGrady, G. Sean; Sirsch, Peter; Chatterton; Nicholas P.; Ostermann, Andreas; Gatti, Carlo Gatti; Altmannshofer, Sandra; Herz, Verena; Eickerling,Georg; Scherer, Wolfgang (2009)
Nature of the Bonding in Metal-Silane sigma-Complexes
in Inorganic chemistry; American Chemical Society, Washington (Stati Uniti d'America)
(literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori

McGrady, G. Sean; Sirsch, Peter; Chatterton; Nicholas P.; Ostermann, Andreas; Gatti, Carlo Gatti; Altmannshofer, Sandra; Herz, Verena; Eickerling,Georg; Scherer, Wolfgang (literal)

Pagina inizio

1588 (literal)

Pagina fine

1598 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume

48 (literal)

Rivista

Inorganic chemistry (Rivista)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#pagineTotali

11 (literal)

Note

ISI Web of Science (WOS) (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni

1. Department of Chemistry, UniVersity of New Brunswick, P.O. Box 4400, Fredericton, N.B. E3B 5A3, Canada, 2. Department of Health and Human Sciences, London Metropolitan UniVersity, 166-220 Holloway Road, London N7 8D8, U.K., 3. Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM-II), Technische UniVersitat Munchen, D-85747 Garching, Germany, 4. CNR-ISTM, Istituto di Scienze e Tecnologie Molecolari, Via C. Golgi 19, 20133 Milano, Italy, 5. Lehrstuhl fur Chemische Physik und Materialwissenschaften, UniVersitat Augsburg, UniVersitatsstr. 1, D-86159 Augsburg, Germany (literal)

Titolo

Nature of the Bonding in Metal-Silane sigma-Complexes (literal)

Abstract

The nature of metal silane ?-bond interaction has been investigated in several key systems by a range of experimental and computational techniques. The structure of [Cp?Mn(CO)2(?2-HSiHPh2)] has been determined by single crystal neutron diffraction, and the geometry at the Si atom is shown to approximate a trigonal bipyramid; salient bond distances and angles are Mn-H(1) 1.575(14), Si-H(1) 1.806(14), Si-H(2) 1.501(13) Å, and H(1)-Si-H(2) 148.5(8)°. This complex is similar to [Cp?Mn(CO)2(?2-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 ?-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) Å in each case, in excellent agreement with the distances deduced from neutron diffraction. Density functional theory calculations have been employed to explore the bonding in the Mn-H-Si unit in 1 and 2 and in the related system [CpetaMn(CO)2(?2-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 f sigma*(X-Si-H) back-donation, which increases with increasing electron-withdrawing 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: the source function S(r,omega), which provides a measure of the relative importance of each atom's contribution to the density at a specific reference point r, clearly shows that all three atoms of the Mn(eta2-SiH) moiety contribute to a very similar extent to the density at the Mn-Si bond critical point, in pleasing agreement with the MO model. Hence, we advance a consistent and unifying concept which accounts for the degree of Si-H activation in these silane sigma-bond complexes. (literal)

Editore