Premium
μ 3 ‐η 2 :η 2 :η 2 ‐Coordination of Primary Silane on a Triruthenium Plane
Author(s) -
Nagaoka Masahiro,
Tsuruda Hiroyuki,
Amako Masaaki,
Suzuki Hiroharu,
Takao Toshiro
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201506969
Subject(s) - silane , chemistry , silylation , ligand (biochemistry) , silanes , tautomer , nuclear magnetic resonance spectroscopy , coordination complex , crystallography , reductive elimination , nmr spectra database , density functional theory , medicinal chemistry , stereochemistry , computational chemistry , spectral line , catalysis , organic chemistry , metal , physics , biochemistry , receptor , astronomy
Abstract A μ 3 ‐η 2 :η 2 :η 2 ‐silane complex, [(Cp*Ru) 3 (μ 3 ‐η 2 :η 2 :η 2 ‐H 3 Si t Bu)(μ‐H) 3 ] ( 2 a ; Cp*=η 5 ‐C 5 Me 5 ), was synthesized from the reaction of [{Cp*Ru(μ‐H)} 3 (μ 3 ‐H) 2 ] ( 1 ) with t BuSiH 3 . Complex 2 a is the first example of a silane ligand adopting a μ 3 ‐η 2 :η 2 :η 2 coordination mode. This unprecedented coordination mode was established by NMR and IR spectroscopy as well as X‐ray diffraction analysis and supported by a density functional study. Variable‐temperature NMR analysis implied that 2 a equilibrates with a tautomeric μ 3 ‐silyl complex ( 3 a ). Although 3 a was not isolated, the corresponding μ 3 ‐silyl complex, [(Cp*Ru) 3 (μ 3 ‐η 2 :η 2 ‐H 2 SiPh)(H)(μ‐H) 3 ] ( 3 b ), was obtained from the reaction of 1 with PhSiH 3 . Treatment of 2 a with PhSiH 3 resulted in a silane exchange reaction, leading to the formation of 3 b accompanied by the elimination of t BuSiH 3 . This result indicates that the μ 3 ‐silane complex can be regarded as an “arrested” intermediate for the oxidative addition/reductive elimination of a primary silane to a trinuclear site.