TY - JOUR
T1 - Reactions of Organocopper Reagents with the Cationic Bridging Acylium Complex [C5H5(CO)Fe]2(μ-CO)(μ-CHCO)+
AU - Casey, Charles P.
AU - Crocker, Mark
AU - Vosejpka, Paul C.
AU - Rheingold, Arnold L.
PY - 1989/2
Y1 - 1989/2
N2 - The bridging acylium complex [C5H5(CO)Fe]2(μ-CO)(μ-CHCO)+PF6- (2) reacted with organocuprates Li(RCuCN) at the acylium carbon to give the acyl-substituted μ-alkylidene complexes [C5H5(CO)Fe]2(μ-CO)(μ-CHCOR) (6, R = CH3; 7, R = (CH2)3CH3; 8, R = C6H5). The acyl groups of complexes 6–8 display low carbonyl stretching frequencies indicative of strong electron donation from the Fe2(μ-C) core onto the acyl substituents. The molecular structure of 8, determined by X-ray crystallography, supports these observations. Crystals of 8 are triclinic, space group PI, with a = 7.008 (2) Å, b = 12.392 (3) Å, c = 12.441 (3) Å, α = 118.37 (2)°, β = 91.09 (2)°, γ = 103.42 (2)°, and Z = 2. 6 reacted with CF3S03CH3 to give the O-methylated complex [C5H5(CO)Fe]2(μ-CO)[μ-CHC(CH3)OCH3]+CF3SO3- (12) resulting from methylation of the acetyl group of 6 at oxygen. Reaction of 2 with Li2[(CH3)2CuCN] afforded the μ-alkenylidene complex [C5H5(CO)Fe]2(μ-CO)[μ-C=(CH3)2] (13) via double nucleophilic addition. 13 reacted with Me3O+BF4- to give the μ-alkylidyne complex [C5H5(CO)Fe]2(μ-CO)[μ-CC(CH3)3]+BF4- (14).
AB - The bridging acylium complex [C5H5(CO)Fe]2(μ-CO)(μ-CHCO)+PF6- (2) reacted with organocuprates Li(RCuCN) at the acylium carbon to give the acyl-substituted μ-alkylidene complexes [C5H5(CO)Fe]2(μ-CO)(μ-CHCOR) (6, R = CH3; 7, R = (CH2)3CH3; 8, R = C6H5). The acyl groups of complexes 6–8 display low carbonyl stretching frequencies indicative of strong electron donation from the Fe2(μ-C) core onto the acyl substituents. The molecular structure of 8, determined by X-ray crystallography, supports these observations. Crystals of 8 are triclinic, space group PI, with a = 7.008 (2) Å, b = 12.392 (3) Å, c = 12.441 (3) Å, α = 118.37 (2)°, β = 91.09 (2)°, γ = 103.42 (2)°, and Z = 2. 6 reacted with CF3S03CH3 to give the O-methylated complex [C5H5(CO)Fe]2(μ-CO)[μ-CHC(CH3)OCH3]+CF3SO3- (12) resulting from methylation of the acetyl group of 6 at oxygen. Reaction of 2 with Li2[(CH3)2CuCN] afforded the μ-alkenylidene complex [C5H5(CO)Fe]2(μ-CO)[μ-C=(CH3)2] (13) via double nucleophilic addition. 13 reacted with Me3O+BF4- to give the μ-alkylidyne complex [C5H5(CO)Fe]2(μ-CO)[μ-CC(CH3)3]+BF4- (14).
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U2 - 10.1021/om00104a002
DO - 10.1021/om00104a002
M3 - Article
AN - SCOPUS:2642662872
SN - 0276-7333
VL - 8
SP - 278
EP - 282
JO - Organometallics
JF - Organometallics
IS - 2
ER -