Acid-catalyzed attack of the dinitrogen ligand in thecis-(Me2PhP)4Mo(N2)2 andtrans-(Ph2PCH2CH2PPh2W(N2)2 complexes by nitronium and nitrosonium cations with the formation of nitrogen oxides

The interaction of labeled dinitrogen complexescis-(Me₂PhP)₄Mo(¹⁵N₂)₂ andtrans-(dppe)₂W(¹⁵N₂)₂ with non-labeled nitronium and nitrosonium fluoroborates,¹⁴NO₂BF₄ and¹⁴NOBF₄, in sulfolane at room temperature in the presence of H₂SO₄ results in rapid formation of labeled nitrous and nitric oxides (¹⁵N¹⁴NO,¹⁵NO), as well as¹⁵N¹⁴N. The yield of the products depends on the reagent ratio and reaches 10–20 mol. % per mole of a complex under optimum conditions. The mechanism of the reactions found is proposed. It involves the step of protonation of the dinitrogen ligand to form the corresponding hydrazido(2–) derivatives, which are then attacked by nitronium or nitrosonium cations. In accordance with the mechanism proposed, it was established that the hydrazido(2–) complexes, (Me₂PhP)₃Mo(¹⁵N₂H₂)Cl₂ and (dppe)₂W(¹⁵N₂H₂)Cl₂, are capable of forming¹⁵N¹⁴NO,¹⁵NO, and¹⁵N¹⁴N under the action of¹⁴NO₂BF₄ and¹⁴NOBF₄ in the absence of an acid.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 13–13, July, 1995.     

Novel Reactions of Organomolybdenum and Organotungsten Compounds: Additive–Reductive Carbonyl Dimerization,Spontaneous Transformation of Methyl Ligands into μ-Methylene Ligands,and Selective Carbonylmethylenation

Hitherto there was no reaction known that permits transformations of R¹R²-CO → 0.5 R¹R²R³C–CR¹R²R³ in one step. This type of additive–reductive carbonyl dimerization is now possible using alkoxy(alkyl)tungsten(v) complexes with aromatic, heteroaromatic or α,β-unsaturated aldehydes and ketones. When a corresponding phenyl complex was employed in a test experiment, it was revealed that an aliphatic ketone could be used as the substrate in this reaction. A second interesting type of reaction is the transformation of CH₃ ligands into μ-CH₂ ligands, which occurs during the treatment of MeLi or Me₃Al with molybdenum or tungsten chlorides (oxidation states VI and V, for Mo additionally IV) at low temperatures with liberation of CH₄. Here, the question arises as to whether the intermediate involved has a terminal CH₂ ligand (Schrock carbene complex) or a μ-CH₃ ligand (CH₃ bound by a two-electron three-center bond to two metal atoms). Of all the μ-CH₂ complexes obtained, those which were synthesized by the action of MeLi on molybdenum chlorides can be recommended as reagents for carbonylmethylenation of aldehydes and ketones. They display high selectivity, very low basicity, a surprising resistance to protons, they are readily available, can be easily modified and, as regards their selective behavior, they have been investigated more thoroughly than other readily accessible carbonylmethylenation reagents of comparable selectivity. The results of NMR spectroscopic investigations on the structure of the μ-CH₂ complexes, and associated reaction mechanisms are discussed. A survey of carbonylmethylenation reagents, which have been reported in the literature, permits comparisons to be made with carbonylmethylenating molybdenum and tungsten complexes.     

丙烯环氧化反应的高活性钼催化剂

在钼(Ⅵ),钒(Ⅴ)和钛(Ⅳ)等化合物存在下,丙烯与烷基过氧化氢的环氧化反应比传统的氯醇法有很多优点,其中以钼催化剂的性能最优,但目前报道的催化剂在反应过程中因易分解而降低了活性,并且丙烯与烷基过氧化氢的投料比过大(>3:1),丙烯循环次数过多。前文报道了钼烷基醇胺化合物对环已烯的环氧化反应,本文考察了钼烷基醇胺化合物对丙烯与叔丁基过氧化氢环氧化反应的催化性能。     

Investigation on the Performance of Supported Molybdenum Carbide for the Partial Oxidation of Methane

The performance of uspported and unsupported molybdenum carbide for the partial oxidation of methane (POM) to syngas was investgated.An evaluation of the catalysts indicates that bulk molybdenum carbied has a higher methane conversion during the initial stage but a lower selectivity to CO and H2/CO ratio in the products.The rapid deactivation of the catalyst is also a significant problem.However,the supported molybdenum carbide catalyst shows a much higher methane conversion,increased selectivity and significantly improved catalytic stability.The characterization by XRD and BET specific area measurements depict an improved dispersion of molybdenum carbide when using alumina as a carrier.The bulk or the supported molybdenum carbide exists in the β-Mo2C phase,while it is transformed into molybdenum dioxide postcatalysis which is an improtant cause of molybdenum carbide deactivation.     

Synthesis and Crystal Structure of Mo(CO)_4(NNP) (NNP=2-(N-Cyclohexyl-N-diphenylphosphinomethyl)aminopyridine)

1 INTRODUCTION The pyridyl-phosphine ligands have been widely used for many years to synthesize hetero- or homo-nuclear metal complexes[1], as electronic differentiation associated with the hard (N) and soft (P) donor atoms dictates their unique reactivities and coordination modes. One of the most common pyridylphosphines studied to date is (2-C5H4N)PPh2 which displays numerous ligating modes ranging from P-coordination and P,N-chelation to the more common P,N-bridging of two metal …     

Regio- and Stereocontrolled Nucleophilic Addition Reactions of An Unsymmetrically Disbustituted Butadiene η4-Molybdenum Cationic Complex

The reactions of a new cationic complex, [Cp(CO)₂Mo(η⁴-2-methyl-3-SPh-C₄H₄)]⁺ PF^?₆ (3), with carbon, hydride, and nitrogen nucleophiles were found to give only the C-1 addition products in good yield. The X-ray crystal structures of two of the addition products 4a and 4e confirm the regio- and stereochemistry of the nucleophilic additions.     

Controllable growth of chains and grids from polyoxomolybdate building blocks linked by silver(I) dimers

Molecular growth processes utilizing a beta-octamolybdate synthon and {Ag2} dimers are described and the directing influence of "encapsulating" cations and coordinating solvent is also demonstrated. The growth of two 1D chains, (nBu4N)2n[Ag2Mo8O26]n (1) and (nBu4N)2n[Ag2Mo8O26(CH3CN)2]n (2), is achieved when nBu4N+ ions are used, and the diameter of the chains can be expanded by the coordination of CH3CN solvent (2). The formation of a type of gridlike structure in which 1D chains are crossed-over each other in alternatively packed layers is achieved in DMSO as the solvent; DMSO acts as a linking group to give (nBu4N)2n[Ag2Mo8O26(dmso)2]n (3), which, similar to 1 and 2, still incorporates the Bu4N+ ions that exert an "encapsulating" influence. However, in (HDMF)n[Ag3(Mo8O26)(dmf)4]n (4) the relatively bulky Bu4N+ ions are exchanged for protonated DMF cations, thereby allowing the chains to condense to a 2D array. The building block concept is further enforced by the isolation of a "monomeric" unit (Ph4P)2[Ag2Mo8O26(dmso)4] (5), which is isolated when the Ph4P+ ions are so "encapsulating" as to prevent aggregation of the {Ag-Mo8-Ag} building blocks. The nature of the AgAg dimers in each of the compounds 1-4 is examined by DFT calculations and the interplay between these Ag-Ag interactions and the structure types is described.     

A radical mechanism of the reaction of molybdenum carbonyl complexes with bis(triethylgermyl)mercury

The reaction of [Cp(CO)₃Mo]₂ with (Et₃Ge)₂Hg occurs in toluene and THF by a radical mechanism. The interaction between [Cp(CO)₃Mo]₂Hg and (Et₃Ge)₂Hg has a radical character only in THF. The formation of Cp(CO)₃MoH at the first stage of these reactions substantially affects the further course of the process.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1648–1650, September, 1993.     

Hydrothermal Synthesis and Structure Characterization of a Novel 4,4′-Bipyridine Bridging Dumbbell-like Dimeric Pentamolybdate

1 INTRODUCTION Polyoxometalates (POMs) have been attracting extensive interest of many chemists in solid-state materials chemistry owning to the various structures and great potential applications in catalysis, medi- cine, photo-electricity and magnetism[1～9]. Over the past decades, lots of novel POMs have been pre- pared by hydrothermal synthesis, such as discrete structure[10], one-dimensional chain-like structure[11, 12] and higher dimensional architecture[13～18]. However, in these…