Reactivity of cyrhetrenylphosphines: Synthesis and characterization of oxides,boranes and selenides |
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| Affiliation: | 1. Instituto de Química y Bioquímica, Universidad de Valparaíso, Av. Gran Bretaña 1111, Valparaíso, Chile;2. Instituto de Química, Pontificia Universidad Católica de Valparaíso, Casilla 4059, Valparaíso, Chile;1. Department of Organic Chemistry, Biochemistry and Catalysis, Faculty of Chemistry, University of Bucharest, Sos. Panduri nr. 90, 050663 Bucharest, Romania;2. Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest, Str. Dumbrava Roşie nr. 23, 020464 Bucharest, Romania;1. School of Chemistry & Chemical Engineering, Xi''an Shiyou University, Xi''an 710065, Shaanxi, PR China;2. School of Chemical Engineering, Shaanxi Key Laboratory of Degradable Medical Material, Northwest University, Xi''an 710069, Shaanxi, PR China;1. Nikolaev Institute of Inorganic Chemistry, 3 Acad. Lavrentiev Ave., Novosibirsk 630090, Russia;2. Novosibirsk State University, 2 Pirogova St., Novosibirsk 630090, Russia;1. Jinzhou Medical University, Jinzhou 121001, PR China;2. MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, PR China |
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| Abstract: | Reaction of cyrhetrenylphosphines, of general formula (η5-C5H4PR2)Re(CO)2L (R = Ph, L = CO (1); R = Cy; L = CO (2); R = Ph, L = PMe3 (3) and R = Ph, L = P(OMe)3 (4)), with H2O2, BH3·THF or selenium gives the respective cyrhetrenylphosphine oxides, boranes and selenides. These species were characterized by standard spectroscopic techniques (FT-IR, 1H and 31PNMR). Based on the 31P 77Se coupling constant (1JP-Se) of the phosphine-selenides, we established the following order of basicity of the parent cyrhetrenylphosphine 2 > 3 > 4 > 1. We also confirmed the opposite electronic effects of the cyrhetrenyl and ferrocenyl groups attached to a –PR2 unit. Finally, phosphine selenides 2c and 4c were structurally characterized by X-ray diffraction. |
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