FORMATION AND PROPERTIES OF SOME CHLORACARBONYL COMPLEXES OF RUTHENIUM (2) AND RUTHENIUM(3)
FORMATION AND PROPERTIES OF SOME CHLORACARBONYL COMPLEXES OF RUTHENIUM (2) AND RUTHENIUM(3)
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DOI：
10.1021/ja00974a020
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发表时间：
1966-01-01
影响因子：
15
通讯作者：
KEMP, ALW
中科院分区：
文献类型：
--
作者：
HALPERN, J;JAMES, BR;KEMP, ALW
根据反应1、11和13，发现一氧化碳与氯钌酸盐（III）和氯钌酸盐（II）络合物在盐酸水溶液中反应以形成羰基衍生物Ru（CO）Cl 52-Ru（CO）（H2O）Cl 42和Ru-（CO）2Cl 42-。研究了这些反应的动力学，并将产物分离为其铵盐并进行了表征。通过三苯基膦与相应阴离子的加成反应，得到了中性衍生物Ru（CO）Cl2（PPh3）3和Ru（CO）2-Cl2（PPh3）2。Ru（CO）-（H2O）Cl 42-也是通过Ru（CO）C152 '与H2的均相还原制备的。发现该反应由于Ru（CO）（H2O）Cl 42-的催化而为自催化的。还发现后者是D2与H2O交换和乙炔水合的催化剂。人们还发现，钌（III）催化的乙炔水合过程中形成的钌碳酰氯络合物，它们的形成伴随着催化活性的下降。
Carbon monoxide was found to react with chlororuthenate (III) and chlororuthenate (II) complexes in aqueous hydrochloric acid solutions to form the carbonyl derivatives Ru (CO) Cl52~ Ru (C0)(H20) Cl42 and Ru-(CO) 2Cl42-, according to reactions 1, 11, and 13. The kinetics of these reactions were examined, and the products were isolated as their ammonium salts and characterized. The neutral derivativesRu (CO) Cl2 (PPh3) 3 and Ru (CO) 2-Cl2 (PPh3) 2 were obtained by addition of triphenylphosphine to solutions of the corresponding anions. Ru (CO)-(H20) Cl42-was also prepared by homogeneous reduction of Ru (CO) C152'with H2. This reaction was found to be autocatalytic due to catalysis by Ru (CO)(H20) Cl42_. The latter was also found to be a catalyst for the exchange of D2 with H20 and for the hydration of acetylene. It was also found that ruthenium carbonyl chloride complexes are formed during the ruthenium (III)-catalyzed hydration of acetylenes and that their formation is accompanied by a fall off of catalytic activity.