Reaction of alkylidenedinitrosylmolybdenum complexes with vinyl trisubstituted silanes and substituted acetylenes

• Published in: Journal of molecular catalysis. A, Chemical Vol. 104; no. 3; pp. 213 - 219
• Main Authors: Keller, A., Matusiak, R.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 1996; Elsevier
• Subjects: Acetylenes; Alkylidene; Catalysis; Catalytic reactions; Chemistry; Exact sciences and technology; General and physical chemistry; Metathesis; Molybdenum; Nitrosyl; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Vinyl silanes; Alkylidene; Acetylenes; Molybdenum; Nitrosyl; Vinyl silanes; Metathesis; Catalytic reaction; Transition metal Nitrosyl Complexes; Acetylenic compound; Molybdenum Nitrosyl Complexes; Polymerization; Organic silane; Experimental study; Acetylene(phenyl) polymer; Catalyst
• ISSN: 1381-1169; 1873-314X
• DOI: 10.1016/1381-1169(95)00150-6

Reaction of Mo(NO) 2 (CHMe) (OR) 2(AlCl 2) (EtAlCl 2) (R = Et, O-i-Pr) with vinyl silanes (vinyltrimethoxysilane and vinyltrimethylsilane) with substituted acetylenes (phenylacetylene and hex-2-yne) are studied. The ethylidene complex has been found to be an efficient catalyst for metathesis reaction of vinyl silanes. 1,2-Bis (trimethoxysilyl) ethene and ethylene are formed, via metathesis of vinyltrimethoxysilane, with a yield of above 80%. Similarly, the self-metathesis of vinyltrimethylsilane in the presence of this complex occurs, yielding 1,2-bis (trimethylsilyl) ethene and ethylene (yield below 20%). The latter reaction was accompanied by a dimerization leading to 1,4-bis (trimethylsilyl) butene-2 which was the prevailing product (above 30%). Trans-cisoidal poly (phenyl acetylene) with low molecular weight, as well as a polymer of hex-2-yne with high molecular weight are produced using this ethylidenemolybdenum complexes. Degradation of the poly (phenylacetylene) by cross-metathesis with vinyltrimethoxysilane was studied, too.