二茂铁单磷钌（II）配合物的制备与表征。[RuH(2)(η(2)-H(2))(PCy(3))2(2-苯基-3,4-二甲基二茂铁膦)]的反应活性、动态溶液行为及X射线结构

Preparation and characterization of ruthenium(II) monophosphaferrocene complexes. Reactivity, dynamic solution behavior, and X-ray structure of [RuH(2)(eta(2)-H(2))(PCy(3))2(2-phenyl-3,4-dimethylphosphaferrocene)].

作者信息

Toner A J, Donnadieu B, Sabo-Etienne S, Chaudret B, Sava X, Mathey F, Le Floch P

机构信息

Laboratoire de Chimie de Coordination du CNRS, 205 Route de Narbonne, 31077 Toulouse Cedex 04, France.

出版信息

Inorg Chem. 2001 Jun 18;40(13):3034-8. doi: 10.1021/ic001404v.

DOI:10.1021/ic001404v

PMID:11399170

Abstract

The bis(dihydrogen) complex RuH(2)(H(2))(2)(PCy(3))(2) (1) reacts with 2-phenyl-3,4-dimethylphosphaferrocene (L(1)) to give RuH(2)(H(2))(PCy(3))(2)(L(1)) (2). This dihydride-dihydrogen complex has been characterized by X-ray crystallography and variable-temperature (1)H and (31)P NMR spectroscopy. The exchange between the dihydrogen ligand and the two hydrides is characterized by a DeltaG() of 46.2 kJ/mol at 263 K. H/D exchange is readily observed when heating a C(7)D(8) solution of 2 (J(H-D) = 30 Hz). The H(2) ligand in 2 can be displaced by ethylene or carbon monoxide leading to the corresponding ethylene or carbonyl complexes. The reaction of 1 with 2 equiv of 3,4-dimethylphosphaferrocene (L(2)) yields the dihydride complex RuH(2)(PCy(3))(2)(L(2))(2) (5).

摘要

双（二氢）配合物RuH₂(H₂)₂(PCy₃)₂ (1) 与2-苯基-3,4-二甲基磷杂茂 (L₁) 反应生成RuH₂(H₂)(PCy₃)₂(L₁) (2)。该二氢化物-二氢配合物已通过X射线晶体学以及变温¹H和³¹P核磁共振光谱进行了表征。在263 K时，二氢配体与两个氢化物之间的交换以46.2 kJ/mol的ΔG⁰为特征。加热2的C₇D₈溶液时很容易观察到H/D交换（J(H-D) = 30 Hz）。2中的H₂配体可被乙烯或一氧化碳取代，生成相应的乙烯或羰基配合物。1与2当量的3,4-二甲基磷杂茂 (L₂) 反应生成二氢化物配合物RuH₂(PCy₃)₂(L₂)₂ (5)。