12176-06-6Relevant articles and documents
Reactions of homo- and heterobinuclear cobalt carbonyls with metal carbonyl hydrides
Kovács, István,Sisak, Attila,Ungváry, Ferenc,Markó, László
, p. 1873 - 1877 (1989)
HMn(CO)5, HMo(CO)3Cp, and HFe(CO)2Cp (Cp = cyclopentadienyl) were found to react with Co2(CO)8 forming HCo(CO)4 and the corresponding mixed-metal carbonyl dimers. It was shown that HMo(CO)3Cp transferred the hydrogen atom to Co2(CO)8 and CoMn(CO)9 in reversible processes. The substituted hydride HMn(CO)4P-n-Bu3 and Co2(CO)8 afforded (CO)4CoMn(CO)4P-n-Bu3 which was characterized by elementary analysis and IR and mass spectroscopy. Its reaction with HMo(CO)3Cp gave HMn(CO)4P-n-Bu3 and CoMo(CO)7Cp. The attack of the hydrides took place in mixed-metal complexes exclusively on the cobalt atom. A mechanism in which the hydrides oxidatively add to a coordinatively unsaturated Co center formed by CO loss is proposed.
THERMOCHEMISTRY OF MOLYBDENUM TRICARBONYL COMPLEXES OF ARENES AND CYCLIC POLYOLEFINS
Hoff, Carl D.
, p. 201 - 214 (1985)
The heats of reaction of arene, cycloheptatriene, and cyclooctatetraene complexes of molybdenum tricarbonyl with pyridine yielding (py)3Mo(CO)3 have been measured by solution calorimetry.Reaction of toluene molybdenum tricarbonyl with cyclopentadiene yielding HMo(CO)3C5H5 and with tetrahydrofuran yielding (THF)Mp(CO)3 have also been studied thermochemically.These measurements yield accurate values for the enthalpy of arene exchange in methylene chloride solution for a number of organomolybdenum complexes.The order of stability: benzene5-c yclopentadienylhydridoa range of 31 kcal/mol.The enthalpy of isomerization of cycloheptatriene to toluene is reduced by 7.1+/-1.2 kcal/mol upon coordination to molybdenum tricarbonyl, indicative of a loss of resonance energy for the complexed arene.The Mo-H bond strength in HMo(CO)3C5H5 is estimated as 66+/-8 kacl/mol.The importance of entropic factors in arene exchange is discussed.
Dinuclear Elimination as a Route to Unusual Bridging Carbonyls and Acetyls in Heterobimetallic Complexes
Marsella, John A.,Huffman, John C.,Caulton, Kenneth G.,Longato, Bruno,Norton, Jack R.
, p. 6360 - 6368 (1982)
Reaction of Cp2ZrMe2 with CpMo(CO)3H yields methane and Cp2ZrMeMo(CO)3Cp (1), which has two terminal carbonyl ligands and a third carbonyl with a low (1545 cm-1) stretching frequency.Added gaseous CO inserts into the Zr-Me bond in 1 to form the
Isolation of two agostic isomers of an organometallic cation: Different structures and colors
Van Der Eide, Edwin F.,Yang, Ping,Bullock, R. Morris
, p. 10190 - 10194 (2013)
Two of a kind: Two agostic isomers of [CpMo(CO)2(PiPr 3)]+ B(C6F5)4- have been isolated. Both were characterized in the solid state by X-ray crystallography and spectroscopic techniques, and also by DFT calculations. Significantly different LUMO energies cause the difference in color (blue versus orange, see picture) of these isomers. Copyright
ARE α-ALKOXYALKYL COMPLEXES SPECIAL? 13C-H COUPLING CONSTANT EVIDENCE
Labinger, Jay A.
, p. 287 - 296 (1980)
Complexes of type LnMCH2O2CCMe3 exhibit relatively large values of 1JCH for the α-carbon; however, unexpectedly large values are also found for the methyl analogs, LnMCH3.Thus this technique does not provide evidence for any unusual
Synthesis of heterodinuclear hydride complexes by oxidative addition of a transition-metal hydride to Pt(0) and Pd(0) complexes
Komine, Nobuyuki,Kuramoto, Ayako,Yasuda, Toshiyuki,Kawabata, Tatsuya,Hirano, Masafumi,Komiya, Sanshiro
, p. 194 - 205 (2015/08/18)
Abstract Heterodinuclear hydridoplatinum and -palladium complexes, (dppe)HPt-MLn (MLn = MoCp(CO)3 (3a), WCp(CO)3 (3b)), (dppe)Pt(μ-H)(μ-CO)Mn(CO)4 (3c), (dppe)Pt(μ-H)(μ-CO)FeCp(CO) (3d), cis-L′2HPt-MLn (5aa: LE' = PPh3; MLn = MoCp(CO)3, 5ba: LE' = PPh3; MLn = WCp(CO)3, 5ab: LE' = PMePh2; MLn = MoCp(CO)3, 5ac: LE' = PMe2Ph; MLn = MoCp(CO)3), (dppe)Pd(μ-H)(μ-CO)MLn (MLn = MoCp(CO)2 (7a), WCp(CO)2 (7b)), (dppe)Pd(μ-H)(μ-CO)Mn(CO)4 (7c) are prepared by the oxidative addition of mononuclear transition-metal hydride complexes to zero-valent platinum or palladium complexes. The reactions of the heterodinuclear hydride complexes 3a, 3d and 7a with electron deficient alkenes and alkynes such as dimethyl fumarate or DMAD cause reductive elimination at the Pt or Pd center to give the Pt(alkene or alkyne)(dppe) and MHLn,, suggesting reversibility of this process. The DFT calculations suggest that these reactions are controlled by the thermodynamic stability and the electron rich alkene complex of Pt(0) (or Pd(0)) are preferable to prepare these heterodinuclear hydride complexes by the oxidative addition.
