The Coordination and Bioinorganic Chemistry of Molybdenum
09 Mar 2007-pp 1-223
About: The article was published on 2007-03-09. It has received 78 citations till now. The article focuses on the topics: Bioorganometallic chemistry & Bioinorganic chemistry.
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TL;DR: In this paper, DFT calculations at the B3LYP level of theory using the pseudo potentials of LANL2DZ and LANL 2TZ (Mo)/6-31G* (C, N, Br, H) and 3-21G basis sets were compared, and results show that the optimized calculated geometry is relatively consistent with the X-ray data and hence the observed structure for the complex is indeed possible.
5 citations
TL;DR: In this article, two cis-dioxomolybdenum(VI) complexes were synthesized in a phenol-based sterically encumbered N2O2 ligand environment and their crystallographic characterizations were reported.
Abstract: Two cis-dioxomolybdenum(VI) complexes [MoO2L] (L: L
1, 2 and L: L
2, 3) in a phenol-based sterically encumbered N2O2 ligand environment have been synthesized, and their crystallographic characterizations are reported. The orange crystals of 2 are monoclinic, space group P21/a with unit cell dimensions as a=16.2407(17) A, b=7.2857(8) A, c=18.400(2) A, β=98.002(9)°, Z=4, and d
cal=1.486 g cm−3. The light orange crystals of 3, however, are orthorhombic, space group, Pbcn, with unit cell dimensions a=8.3110(12) A, b=12.637(3) A, c=34.673(5) A, Z=4, and d
cal=1.187 g cm−3. The structures were refined by a full-matrix least-squares procedure on F
2 to a final R=0.046 (0.055 for 3) using 4944 (3677) all independent data. In both the cases, the Mo atom exists in a distorted octahedral geometry defined by a N2O4 donor set, which features a cis-Mo(–O)2 and a trans-Mo(OPh)2 arrangement. Compound 2 undergoes a quasireversible one-electron reduction at −1.3 V vs Ag/AgCl reference due to MoVIO2/MoVO2 electron transfer and thus providing a rare example of steric solution to the comproportionation–dimerization problem encountered frequently in the development of valid biomimetic models for the active sites of oxomolybdenum enzymes.
5 citations
TL;DR: In this paper, the quasiequilibrium interaction of (hydroxo)oxo-(5,10,15,20-tetraphenylporphynato)molybdenum(V) and piperidine in the toluene medium has been studied by means of chemical kinetics and spectrophotometric titration.
Abstract: The quasiequilibrium interaction of (hydroxo)oxo-(5,10,15,20-tetraphenylporphynato)molybdenum(V) and piperidine in the toluene medium has been studied by means of chemical kinetics and spectrophotometric titration. It has been revealed that the molecular complex formation proceeds as slow irreversible salt formation reaction. It is preceded by the stages of equilibrium substitution of the hydroxo group OH-with piperidine, the outer sphere cationic complex formation [K1 (2.03±0.28)×103 M−1]; and by the coordination of the second piperidine molecule to the cationic complex (K2 1.76±0.39 M−1). The complex formation has been completely kinetically described: the rate equations and rate constants have been derived, and the rate limiting stage has been identified. In addition, the physicochemical data on the intermediates and products are presented. The prospects of application of the mixed porphyrin-containing complex as piperidine receptor, alkaloids and pharmaceuticals building block, have been justified.
5 citations
TL;DR: In this paper, the simultaneous extraction ability of ortho, meta, and para isomers of N,N′-diethyl-N, N′-ditolyl-dipicolinamide (EtTDPA) for molybdenum and technetium were investigated in a large range of nitric and hydrochloric acid conditions.
Abstract: The concentration of molybdenum(VI) in dissolved spent nuclear fuel is comparable with the concentrations of Tc, and the minor actinides (Np, Am). Therefore it is of great interest to understand its behavior under conditions imposed by separation processes. The simultaneous extraction ability of ortho, meta, and para isomers of N,N′-diethyl-N,N′-ditolyl-dipicolinamide (EtTDPA) for molybdenum and technetium were investigated in a large range of nitric and hydrochloric acid conditions. Molybdenum shows no increase in extraction at higher concentrations of nitric acid giving a solvate number n=0 with all isomers of EtTDPA, while Mo shows great extractability from HCl. Technetium distribution ratios decrease with increasing concentrations of nitrate showing indication of ion exchange occurring between TcO4
− and NO3
− anions. Et(m)TDPA and Et(p)TDPA show the greatest extractability, with 60% of the total technetium extracted into the organic phase at 1M HNO3.
4 citations
TL;DR: In this article, the thiocabamoyl-molybdenum complex was characterized by X-ray diffraction analyses, and the geometry around the metal atom of compounds β-3 and 4 were capped octahedrons.
Abstract: Reactions of the thiocarbamoyl-molybdenum complex [Mo(CO)2(η2-SCNMe2)(PPh3)2Cl] 1, and ammonium diethyldithiophosphate, NH4S2P(OEt)2, and potassium tris(pyrazoyl-1-yl)borate, KTp, in dichloromethane at room temperature yielded the seven coordinated diethyldithiophosphate thiocarbamoyl-molybdenum complexe [Mo(CO)2{η2-S2P(OEt)2}(η2-SCNMe2)(PPh3)] β-3, and tris(pyrazoyl-1-yl)borate thiocabamoyl-molybdenum complex [Mo(CO)2(η3-Tp)(η2-SCNMe2)(PPh3)] 4, respectively. The geometry around the metal atom of compounds β-3 and 4 are capped octahedrons. The α- and β-isomers are defined to the dithio-ligand and one of the carbonyl ligands in the trans position in former and two carbonyl ligands in the trans position in later. The thiocabamoyl and diethyldithiophosphate or tris(pyrazoyl-1-yl)borate ligands coordinate to the molybdenum metal center through the carbon and sulfur and two sulfur atoms, or three nitrogen atoms, respectively. Complexes β-3 and 4 are characterized by X-ray diffraction analyses.
3 citations
References
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TL;DR: In this paper, the rate data for the generalized nucleophilic displacement reaction were reviewed, and the authors presented a method to estimate the rate of the generalized displacement reaction in terms of the number of nucleophiles.
Abstract: Recently (1) the rate data for the generalized nucleophilic displacement reaction were reviewed.
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TL;DR: In this article, the preparation of alkyl and aryl π-cyclopentadienyl carbon monoxide or nitric oxide compounds of Cr, Mo, W, and Fe is described.
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