Acyliridium-Alkoxycarbenes and an Iridacycle Containing Vinyl Acetate (−C(CH2)OC(CH3)O−) Ligand from Reactions of Acetatoiridium with Alkynes

Autor:	Hyungeui Lee, Chong Shik Chin, Mieock Kim, and Myung Ki Lee
Rok vydání:	2003
Předmět:	Stereochemistry Ligand Organic Chemistry Alcohol Medicinal chemistry Inorganic Chemistry Metal chemistry.chemical_compound chemistry Deuterium visual_art visual_art.visual_art_medium Vinyl acetate Physical and Theoretical Chemistry Methyl group
Zdroj:	Organometallics. 22:3239-3244
ISSN:	1520-6041 0276-7333
Popis:	Acyliridium-alkoxycarbenes [Ir(C(OR‘)CH3)(C(O)R)(η2-O2CCH3)(PPh3)2]OTf (3, R = CH3, R‘ = CH3 (a), R = CH3, R‘ = CH2CH3 (b), R = CH2Ph, R‘ = CH3 (c), R = CH2Ph, R‘ = CH2CH3 (d)) and (4, R = CH3) are obtained from reactions of [Ir(R)(η2-O2CCH3)(CO)(PPh3)2]OTf (2, R = CH3 (a), CH2Ph (b)) with HC⋮CH/R‘OH and HC⋮CCH2CH2OH, respectively. Complex 2a also undergoes 1,1-insertion reaction of HC⋮CH into an Ir−O bond to give an iridacycle containing a vinyl acetate (−C(CH2)OC(CH3)O−) ligand, (5), in the absence of an alcohol. The methyl group of the alkoxycarbene ligand of 3a is readily transferred to the central metal to give a methyliridium complex and also by PPh3 in solution to give a bis-acyliridium complex. Plausible reaction pathways are suggested for the formation of acyliridium-alkoxycarbenes and the iridacycle containing a vinyl acetate (−C(CH2)OC(CH3)O−) ligand on the basis of the deuterium labeling experiments.
Databáze:	OpenAIRE
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