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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Coordination behaviour in transition metal complexes of asymmetric NPN ligands
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Coordination behaviour in transition metal complexes of asymmetric NPN ligands

机译:非对称NPN配体在过渡金属配合物中的配位行为

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摘要

Two bicyclic, chiral aminophosphine ligands, namely 4R, 9R-1,3-bis(pyridin-2-ylmethyl)-2-(2-propyl)-octahydro-1H-1,3,2-benzodiazaphosphole (1) and 4R, 9R-1,3-bis(pyridin-2-ylmethyl)-2-(2-ethoxy)octahydro-1H-1,3,2-benzodiazaphosphole (2) have been prepared from 1R, 2R-diaminocyclohexane and the appropriate dichlorophosphine and the nature of their coordination to a number of transition metals explored. Ligand 1 coordinates to Pd(II) and Pt(II) as a terdentate donor to give complexes of the type [M(κ~3-N,P,N-1)Cl]~+ whereas ligand 2 favours bidentate κ~2-P,N coordination to give the complexes M(κ~2-P,N-2)Cl_2. The study of the coordination chemistry of the NPN ligand 1 is frustrated by its ready decomposition to an unknown species which appears to be promoted by transition metals. The ligand 2 does not undergo such a transformation and its metal chemistry is more readily examined. Aside from the Pt(II) and Pd(II) complexes above, 2 has been coordinated to Cr(0) and Mo(0) in the octahedral complexes M(κ~2-P,N-2)(CO)_4 and Au(I) in linear Au(κ~1-P-2)Cl. All the complexes have been fully characterised by spectroscopic and analytical techniques including a single-crystal X-ray structure analysis of [Pt(κ~3-N,P,N-1)Cl]Cl, 3.
机译:两个双环手性氨基膦配体,即4R,9R-1,3-双(吡啶-2-基甲基)-2-(2-丙基)-八氢-1H-1,3,2-苯并二氮杂phosph(1)和4R,由1R,2R-二氨基环己烷和适当的二氯膦制备9R-1,3-双(吡啶-2-基甲基)-2-(2-乙氧基)八氢-1H-1,3,2-苯并二氮磷(2)探索了它们与多种过渡金属的协调性质。配体1作为三齿供体与Pd(II)和Pt(II)配合形成[M(κ〜3-N,P,N-1)Cl]〜+类型的配合物,而配体2则倾向于双齿κ〜2 -P,N配位得到配合物M(κ〜2-P,N-2)Cl_2。 NPN配体1易于分解为一种似乎由过渡金属促进的未知物种的过程,使对NPN配体1的配位化学的研究受挫。配体2不经历这种转变,并且其金属化学更容易检查。除了上面的Pt(II)和Pd(II)配合物外,八面体配合物M(κ〜2-P,N-2)(CO)_4和Cr中的2还与Cr(0)和Mo(0)配位。线性Au(κ〜1-P-2)Cl中的Au(I)。所有配合物均已通过光谱学和分析技术充分表征,包括[Pt(κ〜3-N,P,N-1)Cl] Cl,3的单晶X射线结构分析。

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