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.
Carborane Stabilized 19-Electron Molybdenum Metalloradical
Jaiswal, Kuldeep,Malik, Naveen,Tumanskii, Boris,Ménard, Gabriel,Dobrovetsky, Roman
, p. 9842 - 9848 (2021)
Paramagnetic metal complexes gained a lot of attention due to their participation in a number of important chemical reactions. In most cases, these complexes are dominated by 17-e metalloradicals that are associatively activated with highly reactive paramagnetic 19-e species. Molybdenum paramagnetic complexes are among the most investigated ones. While some examples of persistent 17-e Mo-centered radicals have been reported, in contrast, 19-e Mo-centered radicals are illusive species and as such could rarely be detected. In this work, the photodissociation of the [Cp(CO)3Mo]2 dimer (1) in the presence of phosphines was revisited. As a result, the first persistent, formally 19-e Mo radical with significant electron density on the Mo center (22%), Cp(CO)3Mo·PPh2(o-C2B10H11) (5b), was generated and characterized by EPR spectroscopy and MS as well as studied by DFT calculations. The stabilization of 5b was likely achieved due to a unique electron-withdrawing effect of the o-carboranyl substituent at the phosphorus center.
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.
Synthesis and reactivity of diborane(4)yl complexes
Braunschweig, Holger,Koster, Margot
, p. 483 - 487 (2002)
Reaction of various 1,2-dihalodiboranes(4) with Na[(η5-C5H4R)M(CO)3] yielded the diborane(4)yl complexes [X(Me2N)B-B(NMe2){η5-(C5H 4R)M(CO)3}] (5
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
INFRARED MATRIX ISOLATION EVIDENCE FOR THE FORMATION OF (η5-CYCLOPENTADIENYL)TRICARBONYL-MOLYBDENUM AND -TUNGSTEN RADICALS IN CARBON MONOXIDE MATRICES AT 12 K
Mahmoud, Khalil A.,Rest, Antony J.,Alt, Helmut G.
, p. C37 - C41 (1983)
Infrared spectroscopic evidence including 13CO labelling and energy-factored force-field fitting is presented for the first time to show that the radicals (η5-C5H5)M(CO)3 radical (M=Mo, W) and HCO are produced on photolysis of (η5-C5
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
Synthetic and Structural Studies on Group 13 Complexes containing the M(CO)3(η-C5H5) Fragment (M = Cr or Mo). Part 2. Complexes 2>n- (x = 1, n = 0; x = 2, n = 1)
Clarkson, Lucy M.,Clegg, William,Hockless, David C. R.,Norman, Nicholas C.,Farrugia, Louis J.,et al.
, p. 2241 - 2252 (1991)
The synthesis and solution infrared studies of a range of compounds of general formula 2> have been performed where X = Cl or I, L = X, tetrahydrofuran (thf), pyridine (py) and M = Cr, Mo or W.In addition, structures have been determined by X-ray analysis for 2>, 2> and 2> and these are discussed and compared with the structures of related complexes.
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
One-step synthesis and P-H bond cleavage reactions of the phosphanyl complex: Syn -[MoCp{PH(2,4,6-C6H2tBu3)}(CO)2] to give heterometallic phosphinidene-bridged derivatives
Alvarez, M. Angeles,Burgos, Mónica,García, M. Esther,García-Vivó, Daniel,Ruiz, Miguel A.,Vega, Patricia
supporting information, p. 14585 - 14589 (2019/10/16)
Photolysis of [Mo2Cp2(CO)6] and PH2R? (R? = 2,4,6-C6H2tBu3) yielded the title complex, which turned out to be a versatile precursor of novel heterometallic phosphinidene-bridged complexes via three different P-H bond activation processes: photolysis, deprotonation and reduction. In this way the new complexes [MoReCp(μ-PR?)(CO)n] (n = 6,7), [MoFeCp2(μ-PR?)(CO)m], (m = 3, 4) and [MoAuCp(μ-PR?)(CO)2{P(p-tol)3}] were prepared.
