Metal carbonyl chemistry : XIV. Reactions of rhodium carbonyls with ligands |
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| Affiliation: | 1. Department of Energy Science & Engineering, Daegu Gyeongbuk Institute of Science and Technology (DGIST), Daegu 42988, Republic of Korea;2. Department of Applied Chemistry, Kyung Hee University, Yongin, Gyeonggi 17104, Republic of Korea;3. Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China;4. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China;5. Materials and Process Simulation Center, California Institute of Technology, Pasadena, CA 91125, United States;1. Universidad de Buenos Aires, Facultad de Farmacia y Bioquímica, Departamento de Microbiología, Inmunología y Biotecnología/Cátedra de Genética, Buenos Aires, Argentina;2. CONICET-Universidad de Buenos Aires, Instituto de Inmunología, Genética y Metabolismo (INIGEM), Buenos Aires, Argentina;1. Centro de Investigaciones Químicas, Facultad de Ingeniería, Universidad de Carabobo, Valencia, Venezuela;2. Laboratorio PHD, Departamento de Química, Facultad Experimental de Ciencias y Tecnología, Valencia, Venezuela;3. Laboratorio de Química Inorgánica, Departamento de Química, Facultad Experimental de Ciencias, Universidad del Zulia, Maracaibo, Venezuela |
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| Abstract: | Dodecacarbonyltetrarhodium [Rh4(CO)12] reacts with phosphine and phosphite ligands under an atmosphere of nitrogen to give the compounds Rh4(CO)10L2, Rh4(CO)9L3 and Rh4(CO)8L4 [where L = Ph3P or P(OCH2)3CEt (ETPO)1] in which the metal atom cluster is retained. Under similar conditions hexadecacarbonyl-hexarhodium [Rh6(CO)16] reacts with Ph3P, P(OCH2)3CEt or P(OMe)3 to give complexes of the type Rh6(CO)10L6. When the reaction of either Rh4(CO)12 or Rh6(CO)16 with the ligands Ph3P or Ph3As is carried out in the presence of carbon monoxide, breakdown of the metal clusters occurs to give the bridged compounds L2(CO)Rh(CO)2Rh(CO)L2 (where L = Ph3P or Ph3As) in high yields; reaction of Rh4(CO)12 with n-Bu3P under similar conditions gives the compound [(n-Bu3P)3-(CO)Rh]2. Dodecacarbonyltetrarhodium has also been shown to react with PhC2Ph or CF3C2CF3 to give the compounds Rh4(CO)10(RC2R) (R = CF3 or Ph).Some of these ligand-substituted rhodium carbonyls have been shown to be extremely active hydroformylation catalysts for 1-alkenes. |
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