Synthesis and Structure of E-2- (2,4,6-tri-tert-butylphenylphosphinyl ) - 2- [N- (tert-butyldimethylsilyl) - N- (p-chrolophenyl ) ] amino- 1- (2,4,6-tri-tert- butyl-phenyl ) phosphacthylene

The title compound E-2-(2, 4, 6-tri-tert-butylphenylphosphinyl)-2-[ N- ( tert-butyldimethylsilyl )-N- ( p-chrolophenyl )] amino-l- ( 2, 4, 6-tri-tert-butylphenyl)phosphacthylene (C49H78NClP2Si, Mr= 806.65) was synthesized and characterized by X-ray diffraction analysis. The crystal is monoclinic, space group P 21 /n with a=10.319(3), b=23.309(5), c=21.41(1) A, β=99.64(5)°, V=5078(3)A3, Z =4, Dc=1. 05g/cm3, F(000)=1760, μ=1. 92cm-1. Due to the steric hindrance from substituents around phosphaethylene, the P = C bond length is significantly longer than those observed in its analogues. The values of the three bond angles involved in the sp2-hybridized carbon atom (C(1)) of the phosphaethylene are 133.4, 115.1 and 111.4° respectively, deviating significantly from the ideal value of 120°. In addition,although 5 sp2- hybridized atoms (C(2), P(1), C(1), N and C(44)) are sequentially bonded in this molecule, no interaction is observed among the remaining pz orbits of these atoms on the string.     

A new process for preparing dialdehyde by catalytic oxidation of cyclic olefins with aqueous hydrogen peroxide

A. novel peroxo-niobophosphate was synthesized for the first time and used as a catalyst in the oxidation reaction of cyclic olefins with aqueous hydrogen peroxide to prepare dialdehy-des. The catalyst was characterized by elemental analysis, thermographic analyses, IR, UV/vis, 31P NMR and XPS spectra as [ π-C5H5N(CH2 )13 CH3 ]2 [ Nb4O6 (O2 )2 (PO4 )2 ] ·6H2O (PTNP). It showed high selectivity to glutaraldehyde in the catalytic oxidation of cyclopentene with aqueous hydrogen peroxide in ethanol.     

过渡金属有机合物的取代反应

综述了有关金属有机合物取代反应的机理研究以及配体的电子效应,立体效应以及螯合效应等的因素对取代反应的影响。     

4:2钼、钨过氧配合物的制备、结构及其氧化还原分解行为

本文作者曾在用过钨酸分解法制备钨酸的过程中发现, 溶液中W与O2^2^-之比始终为2:1, 这一事实说明溶液中有2:1金属过氧配合物形成, 2:1铂过氧络合物[Mo4O12(O2)2]^4^-文献上已有记载, 但类似的钨配合物尚未见报道。本文制备了这二种配合物, 对比它们的红外和Raman光谱, 并用循环伏安法, 恒电位电解法探讨它们的氧化还原分解体系。     

室温和低酸度条件下钨酸的制备

本文提出了一种在室温(～20℃)和低酸度(～1/V)条件下制备钨酸的新方法,讨论了钨酸的生成机理、化学组成和物理性能。     

Synthesis,reactivity and electrochemical properties of substituted cyclopentadienyl cobalt (Ⅲ) complexes

Cyclopentadienyl cobalt complexes (n5-C5H4R)CoLI2 [L = CO,R=-COOCH2CH=CH2 (3); L=PPh3,R=-COOCH2-CH=CH2 (6); L= P(p-C6H4CH3)3,R=-COOC(CH3) = CH2 (7),-COOCH2C6H5(8),-COOCH2CH = CH2 (9)] were prepared and characterized by elemental analyses,1H NMR,IR and UV-vis spectra.The reaction of complexes (n5-C5H4R)CoLI2[L=CO,R=-COOC(CH3)=CH2 (1) ,-COOCH2C6H5(2):L=PPh3,R =-COOC(CH3)=CH2 (4),-COOCH2C6H5(5)] with Na-Hg resulted in the formation of their corresponding substituted cobaltocene (n5-C5H4R)2Co [R= -COOC(CH3) = CH2 (10),-COOCH2C6H5 (11) ].The electrochemical properties of these complexes 1-11 were studied by cyclic voltammetry.It was found that as the ligand (L) of the cobalt (Ⅲ) complexes changing from CO to PPh3 and P(p-tolyl)3,their oxidation potentials increased gradually.The cyclic voltammetry of α,α'-substituted cobaltocene showed reversible oxidation of one electron pro-