20516-78-3Relevant academic research and scientific papers
Iron carbonyl complexes of triphenylphosphine, triphenylarsine, and triphenylstibine
Clifford,Mukherjee
, p. 151 - 153 (1963)
The preparation in solution at atmospheric pressure of the compounds (C6H5)3MFe(CO)4 and ((C6H5)3M)2Fe(CO)3, where M = P, As, Sb, has been accomplished. The
Important factors in oxygen atom transfer to metal carbonyls. Rate of CO substitution of Cr(CO)6 and Fe(CO)5 in the presence of (p-CH3OC6H4)2EO (E = Se, Te) and of (C6H5)3EO (E = As, Sb). Syntheses and X-ray structure of Cr(CO)5E(p-CH3OC6H4)2
Shen, Jian-Kun,Gao, Yi-Ci,Shi, Qi-Zhen,Rheingold, Arnold L.,Basolo, Fred
, p. 1868 - 1873 (2008/10/08)
An attempt is made to obtain information on the various factors that contribute to the overall O atom transfer rates of reactions of metal carbonyls of the type M-CO + E-O → M + CO2 + E. The metal carbonyls used were Cr(CO)6 and Fe(CO)5, and the O atom transfer reagents were (p-CH3OC6H4)2EO (E = Se, Te), (C6H5)3EO (E = P, As, Sb), and (C6H5)2SO. There was no reaction with either (C6H5)3PO or (C6H5)2SO, under the experimental conditions used. The reagents that did react transfer their O atoms at the relative rates of TeO > SeO > SbO > AsO. These results, along with previously reported data, are discussed in terms of the various important factors believed to contribute to the energetics of these overall reactions. Syntheses are given of the new compounds Cr(CO)5E(p-CH3OC6H4)2 (E = Se, Te), and the X-ray structure of the Te compound is reported. The Cr-Te distance in the present structure, 2.684 (1) ?, is the shortest known, and the Te atom is pyramidal.
Reactivity of Fe(CO)4(H)MPh3 (M = Si, Ge) and mechanism of substitution by two-electron-donor ligands: Implications for the mechanism of hydrosilylation of olefins catalyzed by Fe(CO)5
Bellachioma, Gianfranco,Cardaci, Giuseppe,Colomer, Ernest,Corriu, Robert J. P.,Vioux, André
, p. 519 - 525 (2008/10/08)
cis-Fe(CO)4(H)MPh3 (M = Si, Ge) complexes undergo carbonyl displacement with nucleophilic ligands (phosphines, phosphites) to give Fe(CO)3(H)(L)MPh3. With M = Si the geometry of these complexes depends on the nature of the solvent; in nucleophilic solvents the mer-OC-6-43 isomer is formed, while in nonnucleophilic solvents the mer-OC-6-23 isomer is obtained (the cis positions of H and Si are retained). These two isomers undergo concerted reductive elimination of silane with PPh3. The mer-OC-6-43 isomer reacts 183 ± 19 times faster than the mer-OC-6-23 isomer in toluene at 26.0°C, giving the same 16-electron intermediate; the calculated equilibrium constant for the interconversion of OC-6-43 and OC-6-23 is 823 ± 192 at 26.0°C in toluene. Owing to the strong acidity of Fe(CO)4(H)MPh3 (pKa estimated as 3CN) and of Fe(CO)3(H)(PPh3)MPh3 (pKa estimated as ≤8.94 in CH3CN), reaction with basic two-electron-donor ligands [P(alkyl)3, P(cycloalkyl)3, NR3] leads to the formation of the anionic trigonal-bipyramidal complexes [Fe(CO)4MPh3]- and [Fe(CO)3(L)MPh3]-. cis-Fe(CO)4(H)SiPh3 reacts with isoprene to give [Fe(CO)4SiPh3]2; this reaction is not observed with Fe(CO)3(H)(L)SiPh3. The versatile reactivity of these complexes sheds some light on the mechanism of hydrosilylation of olefins and conjugated dienes. Under thermal conditions previous coordination of the olefin to the metal in this reaction seems to be excluded.
METAL DIMERS AS CATALYSTS. III. THE REACTION BETWEEN Fe(CO)5 AND GROUP V DONOR LIGANDS IN THE PRESENCE OF 5-C5H4R)Fe(CO)2>2 (R = H, Me) AND 5-C5Me5)Fe(CO)2>2 AS CATALYST
Albers, Michel O.,Coville, Neil J.,Singleton, Eric
, p. 261 - 266 (2007/10/02)
The reaction between Fe(CO)5 and Group V donor ligands L, (L = PPh3, AsPh3, SbPh3, PMePh2, PMe2Ph, AsMe2Ph, P(C6H11)3, P(n-Bu)3, P(i-Bu)3, P(OPh)3, P(OEt)3, P(OMe)3) in the presence of 5-C5H4R)Fe(CO)2>2 (R = H, Me) or 5-C5Me5)F
Oxidation of substituted iron carbonyl complexes in acetonitrile, acetone, and dichloromethane at mercury and platinum electrodes
Blanch,Bond,Colton
, p. 755 - 761 (2008/10/08)
The oxidative electrochemistry of the substituted iron carbonyl complexes Fe(CO)4L and Fe(CO)3L2, where L is a monodentate tertiary phosphine, arsine, or stibine ligand, has been studied in acetone, dichloromethane, and acetonitrile at both Hg and Pt electrodes. At platinum electrodes, for L = AsPh3 or SbPh3 the initially generated 17-electron cations [Fe(CO)4L]+ and [Fe(CO)3L2]+ are unstable in all solvents while with phosphorus ligands the species [Fe(CO)3(PPh3)2]+ has some stability in dichloromethane. Reactions leading to decomposition are considered. In marked contrast, at mercury electrodes, the cations appear to be substantially more stable than at platinum, and chemically reversible behavior can be observed where the response is completely irreversible at platinum. The data are explained in terms of a chemically modified pathway at mercury electrodes giving rise to mercury stabilized cations.
THE TRANSITION METAL CATALYZED REACTION BETWEEN Fe(CO)5 AND GROUP V DONOR LIGANDS. A FACILE, HIGH YIELD SYNTHESIS OF Fe(CO)4PPh3
Albers, Michel O.,Coville, Neil J.,Ashworth, Terence V.,Singleton, Eric
, p. 385 - 390 (2007/10/02)
The reaction of Fe(CO)5 and L (L=Group V donor ligand), in the presence of CoCl2 * 2 H2O or CoI2 * 4 H2O as catalyst, results in the synthesis of Fe(CO)4L in good yield.Unusual reactivity patterns for the substitution of CO on Fe(CO)5 by L have been found; for CoI2 as catalyst the reaction rate increases in the order PPh3 ca.AsPh3 ca.P(OPh)3 > SbPh3 > PPh2Me > PPhMe2 > P(C6H11)3 > P(OEt)3 > P(n-Bu)3 > P(OMe)3.These results are interpreted in terms of the variation of the catalyst through interaction of CoX2 with L.
Substitution reaction mechanism of (π-monoolefin)iron tetracarbonyl complexes with group V ligands
Cardaci
, p. 368 - 371 (2008/10/08)
The substitution reactions of Fe(CO)4(CH2=CHPh) with L ligands [L = PPh3, AsPh3, SbPh3, pyridine (py)] are studied in toluene. The reaction with AsPh3, SbPh3, and py gives the monosubstituted complex Fe(CO)4L. The reaction with PPh3 forms simultaneously Fe(CO)4PPh3 and Fe(CO)3(Ph3)2. On the basis of the kinetic results and of the factors influencing the [Fe(CO)4]/[Fe(CO)3L2] ratio, two possible reaction mechanisms are proposed. The influence of the ligand L on the reactivity of the intermediate Fe(CO)4 is reported.
