The photo-induced decarbonylation of Cp ' M(NO)(CO)(2) (M = Cr, Mo, W) with diorgano dichalcogenides (R2E2; E = S, Se; R = Me, Ph)

The photo-induced decarbonylation of Cp'Cr(NO)(CO)(2) (1a) in MeCN solution in the presence of R2E2 (E = S, Se; R = Me, Ph) leads to the formation of chalcogenolato-bridged binuclear complexes Cp-2'Cr-2(NO)(2)(mu -ER)(2) [E = S; R = Me (2a), Ph (3a); E = Se, R = Me (4a), Ph (5a)] while reactions between Cp'M(NO)(CO)(2) [M = Mo (1b), W (1c)] and Ph2E2 (E = S, Se) result in mononuclear complexes Cp'M(NO)(EPh)(2) [M = Mo; E = S (9b), Se (10b); M = W, E = S (11c), Se (12c)]. The corresponding reactions of (1b) with Me2E2 (E = S, Se) yielded both mono and binuclear complexes: Cp'Mo(NO)(SeMe)(2) (8b), Cp-2'Mo-2(NO)(2)(mu -EMe)(2) [E = S (6b), Se (7b)]. The new complexes have been characterized by i.r., H-1-, C-13-n.m.r. spectra and by electron-impact mass spectrometry.

Half-sandwich metal diselenolate complexes Cp#M(NO)(SePh)(2) (M = Mo or W; Cp# = Cp or MeCp) as ligands. Synthesis of selenolate-bridged heterobimetallic compounds

The reactions of half-sandwich diselenolate Mo and W complexes (CpM)-M-#(NO)(SePh)(2) (M = Mo; Cp-# = Cp' (1a), MeCp (1b); M = W; Cp-# = Cp' (1c)) with (Norb)Mo(CO)(4), Ni(COD)(2) and Fe(CO)(5) have been investigated. Treatment of (1a), (1b) and (1c) with (Norb)Mo(CO)(4) in PhMe gave the bimetallic complexes: Cp'Mo(NO)(mu -SePh)(2)Mo(CO)(4) (2a), MeCpMo(NO)(mu -SePh)(2)Mo(CO)(4) (2b) and Cp'W(NO)(mu -SePh)(2)Mo(CO)(4) (2c) in moderate yields. Irradiation of (1a) and (1c) in the presence of Fe(CO)(5) gave heterobimetallic complexes Cp'Mo(CO)(mu -SePh)(2)Fe(CO)(3) (3a) and Cp'W(NO)(mu -SePh)(2)Fe(CO)(3) (3c). Ni(COD)(2) reacts with two equivalents of (1a), (1b) and (1c) to give [Cp'Mo(NO)(mu -SePh)(2)](2)Ni (4a), [MeCpMo(NO)(mu -SePh)(2)](2)Ni (4b) and [Cp'W(NO)(mu -SePh)(2)](2)Ni (4c) in good yields. The new heterobimetallic complexes were characterized by i.r., H-1-n.m.r., C-13-n.m.r. and EI-MS spectroscopy.

Photochemical synthesis and crystal structure of a charge transfer salt [HMDH2][(H2PMoMo11O40)-Mo-v]center dot 2AA center dot 3H(2)O center dot DMF

The title supramolecular compound, [HMDH2][(H2PMoMo11O40)-Mo-V] . 2AA . 3H(2)O . DMF (HMD = hexamethylene diamine; AA=acetaldehyde; DMF=N,N-dimethyl formamide), has been photochemically synthesized by using elemental analysis, IR, solid diffusion reflectance, electronic spectra, ESR spectra and X-ray single-crystal analysis. The crystallographic data: triclinic, P (1) over bar, a=14.092(2), b=14.347(3), c=14.358(3)Angstrom, alpha = 75.10(3), beta = 80.70(3), gamma = 80.73(3)degrees, V = 2746.6(10)Angstrom (3), Z = 2, M-r = 2081.68, D-c=2.517g/cm(3), F(000) =1970, mu (MoK alpha) =2.766mm(-1). The structure has been refined to R =0.0832 and wR=0.2638, by full-matrix least-squares method. The title compound is composed of hexamethylene diamine, two acetaldehyde molecules, three water molecules, one N,N-dimethylformamide and [(H2PMoMo11O40)-Mo-V](2-) heteropoly anion.

The use of half-sandwich iridium dithiolate and diselenolate complexes, Cp*Ir(L)(ER)(2) (L = CO, PMe3, PPh3; ER = SPh, SePh, SeMe), for the synthesis of heterodimetallic compounds. The molecular structure of Cp*Ir(CO)(mu-SePh)(2)[Mo(CO)(4)]

Carbonyl-iridium half-sandwich compounds, Cp*Ir(CO)(EPh)(2) (E = S, Se), were prepared by the photo-induced reaction of Cp*Ir(CO)(2) with the diphenyl dichalcogenides, E2Ph2, and used as neutral chelating ligands in carbonylmetal complexes such as Cp*Ir(CO)(mu-EPh)(2)[Cr(CO)(4)], Cp*Ir(CO)(mu-EPh)(2)[Mo(CO)(4)] and Cp*Ir(CO)(mu-EPh)(2)[Fe(CO)(3)], respectively. A trimethylphosphane - iridium analogue, Cp*Ir(PMe3)(mu-SeMe)(2)[Cr(CO)(4)], was also obtained. The new heterodimetallic complexes were characterized by IR and NMR spectroscopy, and the molecular geometry of Cp*Ir(CO)(mu-SePh)(2)[Mo(CO)(4)] has been determined by a single crystal X-ray structure analysis. According to the long Ir...Mo distance (395.3(1) Angstrom), direct metal-metal interactions appear to be absent. (C) 1998 Elsevier Science S.A. All rights reserved.

Stability of Mo/Si multilayer structure used in Bragg-Fresnel optics

The thermal and chemical stabilities of Mo/Si multilayer structure used in Bragg-Fresnel optics were studied to get optimal technological parameters of pattern generation. Mo/Si multilayers were annealed at temperature ranging from 360 to 770 K, treated with acetone and 5 parts per thousand NaOH solution, and characterized by small-angle x-ray diffraction technique as well as x-ray photoelectron spectroscopy, and Olympus microscopy.

Synthesis and characterization of a new double-cubane Mo-Fe-S cluster compound, [NEt(4)](3)[Mo2Fe6S8(mu-OMe)(3)(SPh)(3)Cl-3]

The new double-cubane cluster compound [NEt(4)](3)[Mo2Fe6S8(mu-OMe)(3)(SPh)(3)Cl-3] is synthesized from (NH4)(2)MoS4, FeCl3, Fe powder, S powder, NaSPh and NEt(4)Br in MeOH-DMF, its crystal structure is determined by X-ray crystallography, and results of XPS indicate a valence state of +4 for Mo.

多组分氧化物Ag－Bi－V－Mo���O催化作用的光电子能谱研究

多组分氧化物Ａｇ－Ｂｉ－Ｖ－Ｍｏ－Ｏ催化作用的光电子能谱研究宋伟，李静，窦伯生（中国科学院长春应用化学研究所长春１３００２２）关键词　钼钒酸铋，助剂Ａｇ，ＸＰＳ，Ａｒ~＋刻蚀，氧化还原对于烃类选择氧化反应中复合氧化物的催化作用，普遍认为是Ｒｅｄｏｘ机...

丙烷氧化反应中多组分氧化物Bi－V－Mo���O催化作用的红外光谱研究

丙烷氧化反应中多组分氧化物Ｂｉ－Ｖ－Ｍｏ－Ｏ催化作用的红外光谱研究李静，宋伟，窦伯生（中国科学院长春应用化学研究所长春１３００２２）关键词钼钒酸铋，丙烷，选择氧化，催化作用机理，红外光谱迄今对于含有钼、铋复合氧化物催化剂的活性中心和作用机理存在不同看...

SEMICONDUCTOR TO METAL TRANSITION IN LN(2)MO(3)O(9) COMPOUNDS

Ln(2)Mo(3)O(12) and Ce2Mo3O12.25 are reduced by hydrogen yielding Mo4+ oxides of the formula Ln(2)Mo(3)O(9) (Ln = La, Ce, Pr, Nd, Sm, Gd and Dy). The new compound Ce2Mo3O9 has the same structure as other Ln(2)Mo(3)O(9) compounds. All of the products are single phase materials and crystallize in a tetragonal scheelite type structure with Mo2O6 clusters. The IR spectra of the Ln(2)Mo(3)O(9) oxides show two absorption bands. These compounds are black n-type semiconductors, and exhibit Curie-Weiss Law behavior from 100K to 250K. Temperature dependence of the electrical properties of these compounds were measured for the first time, and a semiconductor-metal transition was found at about 250 degrees C.

异核双金属离子对配合物［Mo���dtc）_4］·［Nd（dtc）_4］的合成、结

合成了一种新型异核双金属离子对配合物［Ｍｏ（ｄｔｃ）＿４］·［Ｎｄ（ｄｔｃ）＿４］，并通过Ｘ－射线衍射法和元素分析确定了其晶体结构和分子结构，在此基础上，经红外光潜分析确定了该配合物的谱学性质。

STRUCTURE AND CATALYTIC ACTIVITY FOR PROPYLENE OXIDATION OF BI-MO-NB COMPLEX OXIDE CATALYSTS

The structure and catalytic,activity for propylene oxidation of series oxides B2Mo3-3X-Nb2XO12-4X (X=0.00, 0.02, 0.05, 0.10, 0.15, 0.20, 0.25) have been studied by means of XRD, IR, Raman, SEM, ESR and so on. The results showed that in the range of X < 0.

Bi－Mo���Nb复合氧化物催化作用机理的ESR和XPS研究

用ＥＳＲ对比研究了掺杂Ｎｂ对α－Ｂｉ２Ｍｏ３Ｏ（１２）催化剂丙烯还原和氧再氧化的影响，并用ＸＰＳ原位Ａｒ＋溅射研究了催化剂的还原与再氧化过程，观察了上述过程中催化剂内金属离子的价态变化和晶格氧的扩散现象。提出了Ｂｉ－Ｍｏ间通过晶格氧扩散所发生的氧化还原作用及模型，探讨了Ｎｂ（５＋）取代Ｍｏ（６＋）产生的氧空位对加速晶格氧扩散所起的作用。

Bi-Mo-Nb复台氧化物的结构与对丙烯氧化的催化活性

本文用XRD,IR,Raman,SEM和ESR等方法研究了系列氧化物Bi_2Mo_(3-3x)Nb_(2x)O_(12-4x)(X=0.00,0.02,0.05,0.10,0.15,0.20,0.25)的结构和对丙烯氧化的催化活性,结果表明,在X≤0.25范围内,催化剂基本保持典型的α-Bi_2Mo_3O_(12)结构,少量Nb~(5+)的掺杂,可取代晶格中的Mo~(6+),产生氧空位,无序分布的氧空位的浓度先随X值的增加而增加,当X=0.15时达最大值,催化剂对丙烯氧化的催化活性与这种氧空位的浓度成正比,反应遵循Redox机理.