Thiapentadienyl−Rhodium−Phosphine Chemistry1

Autor:	and Monica Shokeen, Eric S. Wise, John R. Bleeke, Nigam P. Rath
Rok vydání:	2006
Předmět:	chemistry.chemical_classification Double bond Ligand Organic Chemistry chemistry.chemical_element Medicinal chemistry Adduct Rhodium Inorganic Chemistry chemistry.chemical_compound chemistry Reagent Organic chemistry Lithium Physical and Theoretical Chemistry Tetrahydrofuran Phosphine
Zdroj:	Organometallics. 25:2486-2500
ISSN:	1520-6041 0276-7333
Popis:	The reactions of (Cl)Rh(PR3)3 (R = Me, Et) with the anionic thiapentadienide reagent lithium 2,3-dimethyl-5-thiapentadienide have been investigated. Treatment of (Cl)Rh(PMe3)3 with lithium 2,3-dimethyl-5-thiapentadienide produces ((1,2,5-η)-2,3-dimethyl-5-thiapentadienyl)Rh(PMe3)3 (1), in which the thiapentadienyl ligand is σ-bonded to rhodium through the sulfur end of the chain and π-bonded through the carbon end (C1−C2 double bond). In solution at room temperature, 1 undergoes a rapid dynamic process involving release and recoordination of the thiapentadienyl double bond C1−C2, causing two of the phosphine ligands to become equivalent. The intermediate in which the double bond C1−C2 is released from the rhodium center can be “trapped” as a dioxygen adduct, ((5-η)-2,3-dimethyl-5-thiapentadienyl)Rh(PMe3)3(η2-O2) (2). When it is stirred at room temperature in tetrahydrofuran solution, 1 slowly rearranges to ((1,4,5-η)-2,3-dimethyl-5-thiapentadienyl)Rh(PMe3)3 (3), the thermodynamic isomer in which the thiap...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::9ff53dfa899cb50ab2087cfdbb945f6d https://doi.org/10.1021/om058058f Zobrazit plný text záznamu