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首页> 外文期刊>Organometallics >Rhodium(I) complexes of a chiral amidophosphine-phosphinite chelate. Dinuclear complexes with chelating and bridging ligands
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Rhodium(I) complexes of a chiral amidophosphine-phosphinite chelate. Dinuclear complexes with chelating and bridging ligands

机译:手性氨基膦-次膦酸酯螯合物的铑(I)络合物。具有螯合和桥联配体的双核配合物

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摘要

Rh(I) complexes of the chiral bidentate ligand (S)-N-diphenylphosphino-2-diphenylphosphinoxy-3,3,N-trimethylbutyramide (1) are reported. Two equivalents of 1 react with [RhCl(1,5-COD)](2) slowly in MeOH to afford an isolable unsymmetrical dinuclear complex [(1)Rh(mu-Cl)(mu-1)Rh(1,5-COD)]Cl (2), and the symmetrical dinuclear compound [Rh(mu-Cl)(1)](2), which exists in two forms, sym-trans (3) and sym-cis (4), in solution. In CD2Cl2 solution, 2 converts slowly to 3 and 4. Two-dimensional exchange spectroscopy on 2 reveals an intramolecular and an intermolecular process during the reaction in CD2Cl2. A second dinuclear cation, [(1)Rh(mu-Cl)(mu-1)Rh(1)](+) (6), containing 3 equiv of 1, can be prepared from the PF6 analogue of 2. [Rh(1,5-COD)(1)]OTf (7a), [RhCl(PPh3)(1)] (8), [Rh(CO)(PPh3)(1)]Cl (9), air-sensitive [Rh(1)(solvent)(2)]OTf (10), and [RhCl(CNBut)(1)] (11) are reported. The solid-state structures for 3 and 7a have been determined by X-ray diffraction. [References: 56]
机译:报道了手性二齿配体(S)-N-二苯基膦基-2-二苯基膦氧基-3,3,N-三甲基丁酰胺(1)的Rh(I)配合物。 2当量的1与[RhCl(1,5-COD)](2)在MeOH中缓慢反应,得到可分离的不对称双核络合物[(1)Rh(mu-Cl)(mu-1)Rh(1,5- (COD)] Cl(2)和对称双核化合物[Rh(mu-Cl)(1)](2),以溶液形式存在,即反式(3)和顺式(4)。 。在CD2Cl2溶液中,2缓慢转换为3和4。2上的二维交换光谱显示在CD2Cl2中的反应过程中存在分子内和分子间过程。可以从2的PF6类似物制备第二个双核阳离子[(1)Rh(mu-Cl)(mu-1)Rh(1)](+)(6),它包含3当量的1。 (1,5-COD)(1)] OTf(7a),[RhCl(PPh3)(1)](8),[Rh(CO)(PPh3)(1)] Cl(9),对空气敏感[报道了Rh(1)(溶剂)(2)] OTf(10)和[RhCl(CNBut)(1)](11)。 3和7a的固态结构已通过X射线衍射确定。 [参考:56]

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