Premium
Remanent Si–H Interactions in Late Transition Metal Silane Complexes
Author(s) -
Hauf Christoph,
BarqueraLozada José E.,
Meixner Petra,
Eickerling Georg,
Altmannshofer Sandra,
Stalke Dietmar,
Zell Thomas,
Schmidt David,
Radius Udo,
Scherer Wolfgang
Publication year - 2013
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201200525
Subject(s) - silane , silanes , hydride , transition metal , oxidative addition , silicon , chemistry , silylation , metal , crystallography , photochemistry , organic chemistry , catalysis
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.