38834-26-3Relevant academic research and scientific papers
Reaction of diiron μ-alkylidyne complexes with diazo compounds
Casey, Charles P.,Austin, Edwin A.,Rheingold, Arnold L.
, p. 2157 - 2164 (2008/10/08)
The reaction of μ-methylidyne complex [(C5H5)(CO)Fe]2(μ-CO)(μ-CH) +PF6- (1) with ethyl diazoacetate gave the ester-substituted μ-alkenyl complex [(C5H5)(CO)Fe]2(μ-CO)(μ-η 1,η2-CH=CHCO2Et)+PF 6- (2) in 86% yield. 1 also reacted with diazomethane, diazoethane, methyl 2-diazopropionate, and (trimethylsilyl)diazomethane to give similar μ-alkenyl products. μ-Alkenyl complex 2 reacted with the nucleophiles NEt4+[HFe(CO)4]- and lithium diethyl malonate to give the carbene complexes [(C5H5)(CO)Fe]2(μ-CO)(μ-CHCH 2CO2Et) (17) and [(C5H5)(CO)Fe]2(μ-CO)(μ-CHCH(CO 2Et)CH(CO2Et)2) (16). Reductive dimerization of 2 gave the tetrairon carbene complex {[(C5H5)(CO)Fe]2(μ-CO)(μ-CHCHCO 2Et)}2. (25). The structure of 25 was determined by X-ray crystallography, monoclinic space group P21/c, with unit cell constants a = 12.318 (2) A?, b = 16.443 (2) A?, c = 17.679 (2) A?, β = 105.20 (1)°, and Z = 4.
The reactions of AgY salts with 4-n(CNMe)n> complexes (Y(1-) = NO3(1-), BF4(1-) or PF6(1-); n = 0, 1 or 2). The crystal structure of BF4
Callan, Brian,Manning, A. R.,Stephens, F. S.
, p. 357 - 378 (2007/10/02)
The oxidative cleavage of 4-n(CNMe)n> (n = 0 - 2) by 2AgX gives mononuclear products.It is shown to be a two-electron process in most solvents but a one-electron process in acetonitrile.The two-electron oxidations proceed by way of adducts such as >BF4 which are isolable when n = 2, detectable when n = 1 and postulated when n = 0.The one-electron process gives no adducts, and 1AgX cleaves all of the substrate to (1+) and . (L = CO or CNMe).The latter may combine or react with added CHBr3 to give .The structure of BF4 has been determined by X-ray diffraction.
BIMETALLIC ACTIVATION OF COORDINATED LIGANDS. REACTIONS OF THE LEWIS ACID (η-C5H5)(CO)3Mo+ PF6- WITH ORGANO-IRON AND -MOLYBDENUM η1-METHOXYMETHYL AND ETHYL COMPLEXES
Markham, James,Tolman, William,Menard, Kevin,Cutler, Alan
, p. 45 - 58 (2007/10/02)
The organometallic Lewis acid Cp(CO)3Mo+ PF6- reacts with organo-iron and -molybdenum methoxymethyl and ethyl complexes via methoxide and/or hydride abstraction.Thus, Cp(CO)3MoCH2OCH3 and Cp(CO)(L)FeCH2OCH3 (L = CO, PPh3) produce the
Iron and molybdenum methylidene compounds (C5H5)(CO)2FeCH2+ and (C5H5)(CO)3MoCH2+PF 6- as alkylating agents toward vinyl, allyl, and acetyl ligands. Preparation and characterization of a molybdenum (methyleneoxy)ethylidene iron compound, (C ...
Bodnar,Cutler
, p. 1558 - 1565 (2008/10/08)
Full title: Iron and molybdenum methylidene compounds (C5H5)(CO)2FeCH2+ and (C5H5)(CO)3MoCH2+PF 6- as alkylating agents toward vinyl, allyl, and acetyl ligands. Preparation and characterization of a molybdenum (methyleneoxy)ethylidene iron compound, (C5H5)(CO)(PPh3)FeC(CH3)OCH 2Mo(CO)3(C5H5)+PF 6-. The methylidene complexes Cp(CO)2Fe=CH2+ (1) and Cp(CO)3MoCH2+PF6- (2) are used as alkylating agents toward coordinated ligands. Thus, 1 adds to the uncoordinated double bonds of FpCH=CH2 and FpCH2CH=CH2 (Fp = Cp(CO)2Fe) to give the homologated Fp2 salts [FpCH2]2CH+ and Fp[CH2= CHCH2CH2Fp]+. The former salt arises from electrophilic attack of 1 on the vinylic β-carbon, followed by isomerization of the resulting alkylidene intermediate FpCH+CH2CH2Fp to the observed Fp2 β-carbonium ion salt. The acetyl complex Cp(CO)(PPh3)FeCOCH3 (4), but not FpCOCH3, also undergoes alkylation by 1. A partially characterized [(methyleneoxy)ethylidene]iron, Cp(CO)(PPh3)FeC(CH3)OCH2Fp+ (16), results that readily degrades to the μ-acetyl compound Cp(CO)(PPh3)FeC(CH3)OFp+PF6 - as the major product. Use of the more electrophilic 2 converts 4 to the fully characterized adduct Cp(CO)(PPh3)-FeC(CH3)OCH2Mp+PF 6- (5) (Mp = Cp(CO)3Mo). Reactions of nucleophiles (I-, Cl-, various hydride donors) with 5 displace the starting acetyl complex 4 and leave the corresponding molybdenum methyl complex.
