TY - JOUR
T1 - Reactions of Heteroatom and Carbon Nucleophiles with the Cationic Bridging Methylidyne Complex {[C5H5)(CO)Fe]2(μ-CO)(μ-CH)}+PF6-
AU - Casey, Charles P.
AU - Crocker, Mark
AU - Vosejpka, Paul C.
AU - Fagan, Paul J.
AU - Marder, Seth R.
AU - Gohdes, Mark A.
PY - 1988/3
Y1 - 1988/3
N2 - The reaction of the μ-methylidyne complex {[(C5H5)(CO)Fe]2(μ-CO)(μ-CH)|+PF6- (1) with NMe3 and (C6H5)2C=NH gave the cationic 1:1 adducts ([(C5H5)(CO)Fe]2(μ-CO)(μ-CHNMe3)}+PF6- (3) and {[(C5H5)(CO)Fe]2(μ-CO)[μ-CHNH==C(C6H5)2])+PF6- (9), respectively, arising from attack of nitrogen on the methylidyne carbon. The reaction of 1 with KOC(CH3)3 gave the neutral μ-carbene complex [(C5H6)(CO)Fe]2(μ-CO)[μ-CHOC(CH3)3] (4). Reaction of 1 with water afforded a 1:1 mixture of μ-methylene complex [(C5H5)(CO)Fe]2(μ-CO)(μ-CH2) (2) and [(C5H5)(CO)Fe]2(μ-CO)2; these products are proposed to arise from disproportionation of an initially formed hydroxy carbene species. Reaction of 1 with Et4N+Br- gave the unstable μ-carbene complex [(C6H5)(CO)Fe]2(μ-CO)(μ-CHBr) (6). Reaction of 1 with the carbon nucleophiles CH3Li and Li(C6H5CuCN) gave the μ-carbene complexes [(C5H5)(CO)Fe]2(μ-CO)(μ-CHCH3) (11) and [(C6H5)(CO)Fe]2(μ-CO)(μ-CHC6H5) (12), while reaction of 1 with HFe(CO)4- afforded 2. 1 reacted with acetone via nucleophilic addition of the enol affording the neutral μ-carbene complex [(C6H5)-(CO)Fe]2(μ-CO)(μ-CHCH2COCH3)] (13). 1 also reacted with cyclohexanone, 2-butanone, 4-methyl-2-pentanone, 2,4-pentanedione, 5,5-dimethyl-1,3-cyclohexanedione, ethyl acetoacetate, and the sodium salt of diethyl malonate to give similar μ-carbene products.
AB - The reaction of the μ-methylidyne complex {[(C5H5)(CO)Fe]2(μ-CO)(μ-CH)|+PF6- (1) with NMe3 and (C6H5)2C=NH gave the cationic 1:1 adducts ([(C5H5)(CO)Fe]2(μ-CO)(μ-CHNMe3)}+PF6- (3) and {[(C5H5)(CO)Fe]2(μ-CO)[μ-CHNH==C(C6H5)2])+PF6- (9), respectively, arising from attack of nitrogen on the methylidyne carbon. The reaction of 1 with KOC(CH3)3 gave the neutral μ-carbene complex [(C5H6)(CO)Fe]2(μ-CO)[μ-CHOC(CH3)3] (4). Reaction of 1 with water afforded a 1:1 mixture of μ-methylene complex [(C5H5)(CO)Fe]2(μ-CO)(μ-CH2) (2) and [(C5H5)(CO)Fe]2(μ-CO)2; these products are proposed to arise from disproportionation of an initially formed hydroxy carbene species. Reaction of 1 with Et4N+Br- gave the unstable μ-carbene complex [(C6H5)(CO)Fe]2(μ-CO)(μ-CHBr) (6). Reaction of 1 with the carbon nucleophiles CH3Li and Li(C6H5CuCN) gave the μ-carbene complexes [(C5H5)(CO)Fe]2(μ-CO)(μ-CHCH3) (11) and [(C6H5)(CO)Fe]2(μ-CO)(μ-CHC6H5) (12), while reaction of 1 with HFe(CO)4- afforded 2. 1 reacted with acetone via nucleophilic addition of the enol affording the neutral μ-carbene complex [(C6H5)-(CO)Fe]2(μ-CO)(μ-CHCH2COCH3)] (13). 1 also reacted with cyclohexanone, 2-butanone, 4-methyl-2-pentanone, 2,4-pentanedione, 5,5-dimethyl-1,3-cyclohexanedione, ethyl acetoacetate, and the sodium salt of diethyl malonate to give similar μ-carbene products.
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U2 - 10.1021/om00093a016
DO - 10.1021/om00093a016
M3 - Article
AN - SCOPUS:0012712891
SN - 0276-7333
VL - 7
SP - 670
EP - 675
JO - Organometallics
JF - Organometallics
IS - 3
ER -