In:
Zeitschrift für anorganische und allgemeine Chemie, Wiley, Vol. 639, No. 11 ( 2013-09), p. 1996-2004
Abstract:
In general, it is assumed that the reaction between silanes and late transition metal fragments yields silyl hydride species as oxidative addition products. However, the silane complex Ni( i Pr 2 Im) 2 (SiHMePh 2 ) ( i Pr 2 Im = 1, 3‐diisopropylimidazolin‐2‐ylidene) ( 3a ), might represent one of the rare systems where a stable η 2 ‐(Si–H)Ni intermediate of the oxidative addition process has been isolated. Indeed, 3a is characterized by an acute [ang]Si–Ni–H angle of 62.0(2)°, a rather short Si–H bond length of 1.992(6) Å and displays a silicon‐hydride cross peak in Si‐H‐HMQC 2D‐NMR studies. We therefore selected the latter system for a combined experimental and theoretical charge density study to explore the electronic prerequisites which hinder the full completion of the oxidative addition step in transition metal silane complexes and cause the presence of remanent Si–H interactions in these species.
Type of Medium:
Online Resource
ISSN:
0044-2313
,
1521-3749
DOI:
10.1002/zaac.v639.11
DOI:
10.1002/zaac.201200525
Language:
English
Publisher:
Wiley
Publication Date:
2013
detail.hit.zdb_id:
201094-X
detail.hit.zdb_id:
1481139-X
Bookmarklink