Synthesis, Structures, and Reactivity of Ruthenium(II) Nitrosyl Tri- and Dialkyl Complexes

Autor:	Ian D. Williams, Wa-Hung Leung, Ka-Wang Chan, Enrique Kwan Huang
Rok vydání:	2009
Předmět:	chemistry.chemical_classification Stereochemistry Organic Chemistry Infrared spectroscopy chemistry.chemical_element Protonation Ruthenium Adduct Inorganic Chemistry chemistry Reactivity (chemistry) Physical and Theoretical Chemistry Trifluoromethanesulfonate Alkyl
Zdroj:	Organometallics. 28:5794-5801
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om900598j
Popis:	Treatment of Ru(dtbpy)(NO)Cl3 (dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridyl) (1) with Me3SiCH2MgCl afforded the trialkyl compound mer-Ru(dtbpy)(NO)(CH2SiMe3)3 (2), which exhibits νNO at 1741 cm−1 in the IR spectrum. The solid-state structure of 2 shows a mer arrangement for the three alkyl groups and that the nitrosyl is trans to dtbpy. Protonation of 2 with HX afforded the dialkyl compounds cis,cis-Ru(dtbpy)(CH2SiMe3)(NO)X (X = Cl (3), OTs (4)), in which X is trans to an alkyl group. Treatment of 3 with AgOTf (OTf− = triflate) afforded cis,cis-Ru(dtbpy)(CH2SiMe3)2(NO)(OTf) (5), which reacted with amines RNH2 to give the adducts cis,cis-[Ru(dtbpy)(CH2SiMe3)2(NO)(NH2R)][OTf] (R = meistyl (6), 4-tol (7)). Substitution of 5 with NaOR led to the isolation of cis,trans-Ru(dtbpy)(CH2SiMe3)2(NO)(OR) (R = Ph (8), SiMe3 (9), SiPh3 (10)), in which the nitrosyl is trans to OR−, whereas that with NaSR gave cis,cis-Ru(dtbpy)(CH2SiMe3)2(NO)(SR) (R = 2,6-Me2C6H4 (11), SiPh3 (12)). Treatment of 5 with K[OsO3N] afforded the ...
Databáze:	OpenAIRE
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