Stoichiometric Reaction Chemistry of Cationic Ruthenium Silylene Complexes toward Polar and Nonpolar Organic Substrates

Autor:	T. Don Tilley, Meg E. Fasulo
Rok vydání:	2012
Předmět:	Stereochemistry Chemistry Organic Chemistry Cationic polymerization Silylene chemistry.chemical_element Medicinal chemistry Ruthenium Styrene Inorganic Chemistry chemistry.chemical_compound Polar Cyclopentene Lewis acids and bases Physical and Theoretical Chemistry Stoichiometry
Zdroj:	Organometallics. 31:5049-5057
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om300390n
Popis:	Reactions of the cationic ruthenium silylene complexes [Cp*(PiPr3)Ru(H)2(═SiRR′)][B(C6F5)4] (R = Mes, R′ = H, 1; R = R′ = Ph, 2) with alkenes, alkynes, ketones, and Lewis bases were explored. Addition of 1-hexene, 3,3-dimethylbut-1-ene, styrene, and cyclopentene to 1 afforded the disubstituted silylene products [Cp*(PiPr3)Ru(H)2(═SiMesR)][B(C6F5)4] (R = Hex, 3; R = CH2CH2tBu, 4; R = CH2CH2Ph, 5; R = C5H9, 6). Analogous reactions with 2-butyne and 3,3-dimethylbut-1-yne yielded the vinyl-substituted silylene complexes [Cp*(PiPr3)Ru(H)2(═Si(CR═CHR′)Mes)][B(C6F)4] (R = R′ = Me, 7; R = H, R′ = tBu, 8). Complex 1 undergoes reactions with ketones to give the heteroatom-substituted silylene complexes [Cp*(PiPr3)Ru(H)2(═Si(OCHPhR)Mes)][B(C6F)4] (R = Ph, 9; R = Me, 10). Interestingly, complexes 3–8 display a weak interaction between the hydride ligands and the silicon center, while 9 and 10 exhibit a relatively large interaction (as determined by 2JSiH values). The reaction of isocyanates with 1 resulted in the sil...
Databáze:	OpenAIRE
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