12126-18-0Relevant articles and documents
Electrochemical Behaviour of Mixed Tetrametallic Clusters with Pd2M2 and Pt2M2 Cores (M = Cr, Mo, W)
Jund, Rodolphe,Lemoine, Paul,Gross, Maurice,Bender, Robert,Braunstein, Pierre
, p. 86 - 88 (1983)
Tetrametallic clusters 1M2(μ3-CO)(μ2-CO)2(C5H5)(PPh3)>2 (M1 = Pd, Pt; M2 = Cr, Mo, W) exhibit an unexpected irreversible two-electron reduction leading to the rupture of the metallic core
Selective additions of group 11 and 12 metal fragments to the Fe4C and Fe5C units
Camats, Joan,Reina, Roser,Riba, Olga,Rossell, Oriol,Seco, Miquel,Gómez-Sal, Pilar,Martín, Avelino,De Montauzon, Dominique
, p. 3316 - 3322 (2000)
A selective site of interaction has been observed in reacting HgM+ or M′PPh3+ (M = Mo(CO)3Cp, W(CO)3Cp; M′ = Au, Cu, Ag) with [Fe4C(CO)12{HgM}]- to give the mixed-transition-metal clusters [Fe4C(CO)12{HgM}2] and [Fe4C(CO)12{HgM}{M′PPh3}], respectively. The reaction of [Fe5C(CO)14{HgM}]- with M′PPh3+ permits us to obtain the very unstable neutral octanuclear [Fe5C(CO)14{HgM} {M′PPh3}] clusters. The new compounds have been studied by VT-NMR and Mossbauer spectroscopy. The electrochemical behavior of the Fe4C derivatives has been investigated, and an X-ray crystal structure determination of the complex [Fe4C(CO)12{HgMo(CO)3Cp} {AuPPh3}] has been carried out.
Reactions of dinuclear and polynuclear complexes XVI. Chemistry of hydrido-, thiolato-bridged complexes [Mo2Cp2(μ-H)(μ-SR)(CO)4](R = Me, Ph): Reactivity and electrochemical behaviour; crystal structure of [Mo2Cp2(μ-SPh) {μ-σ:η2-C(CH3) =CHCH3}(CO)2]1
Schollhammer, Philippe,Petillon, Francois Y.,Poder-Guillou, Sylvie,Talarmin, Jean,Muir, Kenneth W.,Yufit, Dmitri S.
, p. 181 - 192 (2007/10/03)
Photolysis of [Cp2Mo2(μ-H)(μ-ER)(CO)4] (ER = SMe (1) or SPh (2)) with MeC≡CMe gives the μ-vinyl complex [Cp2Mo2{μ-σ:η2-C(CH3)=CHCH3}(μ-ER)(CO)2] (ER = SMe (5) or SPh (6)) as the major product. Partial oxidation of 5 leads to the oxo compound [Cp2Mo2(O) {μ-σ:η2-C(CH3)=CHCH3}(μ-SR)(CO)] (7) with a low yield. Compound 6 has been structurally characterized by X-ray diffraction. The structure contains μ-σ:η2-C(CH3)=CHCH3 bridging an Mo=Mo double bond whose length is 2.644(1) A. Chemical deprotonation of [Cp2Mo2(μ-H)(μ-ER)(CO)4] (1 or 2) affords the anionic complex [Cp2Mo2(μ-ER)(CO)4]- (R = SMe (8) and SPh (9)), which is also obtainable by electrochemical reduction. The fluxional behaviour of 8 and 9 and the mechanism of reduction of 1-4 (ER = StBu(3) or SePh(4)) are described.
Electron and bromine transfer reactions between metal carbonyl anions and metal carbonyl bromides. Crystal and molecular structure of dimeric indenyl molybdenum tricarbonyl
Striejewske, William S.,See, Ronald F.,Churchill, Melvyn Rowen,Atwood, Jim D.
, p. 4413 - 4419 (2008/10/08)
Reactions of metal carbonyl anions with metal carbonyl halides proceed by two separate paths. When the reactant anion is a strong nucleophile, the halogen is transferred, resulting in a new metal carbonyl halide and a new metal carbonyl anion as intermediates. The ultimate products, in this case, are the homobimetallic complexes. In cases where the reactant metal carbonyl anion is a poor nucleophile, a single electron transfer occurs, leading to the two homobimetallic complexes and to the heterobimetallic complex. Halide effects and possible indenyl effects are examined. The complex [Mo(indenyl)(CO)3]2 crystallizes in the noncentrosymmetric orthorhombic space group P212121 (No. 19) with a = 7.3572(7) ?, b = 14.4539(12) ?, c = 19.983(2) ?, V = 2125.0(4) ?3, and Z = 4. Diffraction data were collected on a Siemens R3m/V diffractometer for 2θ = 5-45° (Mo Kα), and the structure was solved and refined to R = 3.21% and Rw = 3.23% for all 2786 independent reflections (R = 2.26% and Rw = 2.81% for those 2314 reflections with |Fo|> 6σ(|Fo|). The complex is held together by a Mo-Mo single bond (Mo(1)-Mo(2) = 3.251(1) ?), and has Mo-CO distances ranging from 1.956(6) to 1.988(7) ?, averaging 1.970 ± 0.016 A. Molybdenum-carbon distances to the η5-indenyl rings range from 2.300(7) to 2.427(6) ? for Mo(1) and 2.306(7) to 2.430(6) ? for Mo(2).
Metalloporphyrins with metal-metal bonds. Synthesis, characterization, and electrochemistry of (P)TlMn(CO)5, (P)TlCo(CO)4, and (P)TlM(CO)3Cp where M = Cr, Mo, and W. Crystal structure of [(2,3,7,8,12,13,17,18-octaethylporphinato)thallium(III)]pentacarbonylmanganese
Guilard,Zrineh,Ferhat,Tabard,Mitaine,Swistak,Richard,Lecomte,Kadish
, p. 697 - 705 (2008/10/08)
The synthesis, physicochemical properties, and electrochemistry of a new series of metal-metal σ-bonded thallium porphyrins are reported. The metalate ligands σ-bonded to the thallium octaethyl- or tetraphenylporphyrin complexes were Mn(CO)5, Co(CO)4, W(CO)3Cp, Mo(CO)3Cp, and Cr(CO)3Cp. Each neutral complex was characterized by 1H NMR, IR, and UV-visible spectroscopy, all of which suggested a single metal-metal covalent bond. The crystal structure of (OEP)TlMn(CO)5 was also solved (triclinic, P1, a = 12.467 (2) A?, b = 13.528 (2) A?, c = 15.088 (3) A?, α = 62.04 (2)°, β = 61.62 (2)°, γ = 69.53 (2)°, Z = 2, R(F) = 0.027, Rw(F) = 0.033, w = (σ2(I) + 0.04I)-1). The σ Tl-Mn bond length is 2.649 (1) A?. Electrochemistry and spectroelectrochemistry techniques were used to characterize each oxidized and reduced complex in methylene chloride containing 0.1 M tetrabutylammonium hexafluorophosphate as supporting electrolyte. Each complex underwent two oxidations, which were centered at the porphyrin π ring system. Unlike the case for metal-metal-σ-bonded indium porphyrins, no cleavage of the σ-bond occurs following the first oxidation; i.e., the generated radical cations are stable on the cyclic voltammetry time scale. The metal-metal-bonded compounds could also be reduced by two one-electron additions, but the generated anion radical stability was very low. The ultimate products of electroreduction were the free base porphyrin radical anion and a bis(thallium(I)) compound that was formed from a transient mono(thallium(I)) porphyrin complex.
