Electrochemical, electron spin resonance and nuclear magnetic resonance investigations of tertiary phosphine complexes of nickel. Part 2. [Ni<sup>I</sup>L<sub>4</sub>]<sup>+</sup>, [Ni<sup>I</sup>(L–L)<sub>2</sub>]<sup>+</sup>and their precursors (L = monodentate phosphine, L–L = bidentate diphosphine)
作者:Graham A. Bowmaker、Julian P. Williams
DOI:10.1039/dt9940001231
日期:——
Electrochemical studies of the above complexes in CH2Cl2 and of CH2Cl2 solutions containing nickel(II) and an excess of ligand L = PMePh2 or PBunPh2 or L–L = C6H4(PMePh)2-1,2 have been made. Two successive one-electron metal-based reductions were observed for the [Ni(L–L)2]2+ complexes. The halide-containing complexes showed complex redox behaviour involving loss of halide upon one-electron reduction
复合物[Ni(L–L)2 ] 2+和[NiX(L–L)2 ] + [L–L =顺式-C 2 H 2(PPh 2)2 -1,2,C 6 H 4( PPh 2)2 -1,2,C 6 H 4(PMePh)(PPh 2)-1,2或C 6 H 4(PBu n Ph)(PPh 2)-1,2; X = Cl或Br]已经制备并表征。磷31 NMR光谱显示[Ni(L–L)2 ] 2+的立体异构体的存在当L–L被不对称取代时,L–L = C 6 H 4(PBu n Ph)(PPh 2)-1,2的结果将被给出和分析。在CH上述复合物的电化学研究2氯2和CH的2氯2个溶液含有镍(II)和过量的配位体L = PMePh的2或PBU Ñ博士2或L-L = C 6 H ^ 4(PMePh)2 -1,2已制成。[Ni(L–L)2 ] 2+连续两次基于单电子金属的还原复合体。含卤化物的配合物表现出复杂的氧化还原行为,涉及单电子还原形成稳定的[Ni
Electrochemical, electron spin resonance and nuclear magnetic resonance investigations of tertiary phosphine complexes of nickel. Part 1. Mono- and di-nuclear nickel dithiolene and nickel dihalide species
作者:Graham A. Bowmaker、Julian P. Williams
DOI:10.1039/dt9930003593
日期:——
dinuclear complexes (n= 2) exhibited multiple redox processes. The ESR spectra show that the reduction products involve metal-based electron addition yield the corresponding nickel(I) species, while the oxidation products involve removal of a primarily ligandbased electron. The one-electron reduction product of the complex [Ni(S2C2Ph2)C6H4(PMePh)2-1,2}] shows a spectrum characteristic of a nickel(I) monomer
合成,表征和31个[镍S的P NMR参数2 Ç 2(CN)2 }(PR 3)2 ](PR 3 = PMePh 2或PBU Ñ博士2)和[的Ni(S 2 c ^ 2 R 2)(L–L)} n ]络合物(L–L =含有亚乙烯基或邻亚苯基间磷键的二叔膦,n = 1或2,R = CN或Ph)。[Ni(S 2 C 2 R 2)(L–L)}}的31 P NMR数据n ]配合物表明,环对化学位移的贡献很大,单核物种为正(n= 1),双核物种接近零或为负(n= 2)。配合物的电化学研究及其电生成产物的ESR研究表明,由于(i)配位环大小,(ii)磷间键合和(iii)磷取代基的变化,电化学和ESR参数也发生了变化。氧化还原产物的ESR光谱标识为[Ni S 2 C 2(CN) 2 } C 6 H 4(PMePh)(PPh 2)-1,2}}。+表现出两个化学上不等价的31 P核。双核配合物( n =
Method for the production of amines by reductive amination of carbonyl compounds under transfer-hydrogenation conditions
申请人:——
公开号:US20040267051A1
公开(公告)日:2004-12-30
The invention relates to the production of amines by the reaction of aldehydes or ketones with ammonia or primary or secondary amines in the presence of a hydrogen-donor and the presence of homogeneous metal catalysts of the eighth sub-group under mild conditions.