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Photochemically Induced Silicon−Carbon Bond Cleavage in a Dimethylsilyl‐Bridged Dicyclopentadienyl Diruthenium Complex
Author(s) -
Fox Thomas,
Burger Peter
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200103)2001:3<795::aid-ejic795>3.0.co;2-7
Subject(s) - chemistry , crystallography , cleavage (geology) , silicon , metal , crystal structure , density functional theory , metal carbonyl , stereochemistry , photochemistry , computational chemistry , organic chemistry , geotechnical engineering , fracture (geology) , engineering
The synthesis and X‐ray crystal structure of the novel permethylated dimethylsilyl‐bridged diruthenium complex Me 2 Si[(C 5 Me 4 )Ru(CO) 2 ] 2 (1) is reported. The molecular structure displays a metal−metal bond of 2.7121(4) Å, which is supported by two symmetrical μ‐bridging CO groups and, in addition, two terminal carbonyl ligands. In solution, exchange of these carbonyl groups is observed, as shown by 13 C NMR EXSY and VT IR‐measurements. It is suggested that the exchange process proceeds via the energetically disfavoured intermediate 1a , which displays four terminal CO ligands. This view is supported by density functional calculations, which indicate a C 2 ‐symmetrical structure for 1a . Photochemically induced cleavage of the silicon−carbon and Ru−Ru bonds in 1 results in complex 3 , which is thermodynamically uphill from 1 according to our DFT calculations. The molecular structure of complex 3 was unambiguously confirmed by X‐ray crystallography.