Synthesis and molecular structures of dinuclear complexes with 1,2-dihydro-1,2-diphenyl-naphtho[1,8-c,d]1,2-diphosphole as a bridging ligand |
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Authors: | Mizuta Tsutomu Kunikata Satoru |
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Institution: | Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8526, Japan |
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Abstract: | A bisphosphine in which a PhP-PPh bond bridges 1,8-positions of naphthalene, 1,2-dihydro-1,2-diphenyl-naphtho1,8-cd]-1,2-diphosphole (1), was used as a bridging ligand for the preparation of dinuclear group 6 metal complexes. Free trans-1, a more stable isomer having two phenyl groups on phosphorus centers mutually trans with respect to a naphthalene plane, was allowed to react with two equivalents of M(CO)5(thf) (M = W, Mo, Cr) at room temperature to give dinuclear complexes (OC)5M(μ-trans-1)M(CO)5 (M = W (2a), Mo (2b), Cr (2c)). The preparation of the corresponding dinuclear complexes bridged by the cis isomer of 1 was also carried out starting from the free trans-1 in the following way. Mono-nuclear complexes M(trans-1)(CO)5 (M = W (3a), Mo (3b), Cr (3c)) which had been prepared by a reaction of trans-1 with one equivalent of the corresponding M(CO)5(thf) (M = W, Mo, Cr) complex, were heated in toluene, wherein a part of the trans-3a-c was converted to their respective cis isomer M(cis-1)(CO)5. Each cis trans mixture of the mono-nuclear complexes 3a-c was treated with the corresponding M(CO)5(thf) to give a cis trans mixture of the respective dinuclear complexes 2a-c. The cis isomer of the ditungsten complex 2a was isolated, and its molecular structure was confirmed by X-ray analysis, showing a shorter W?W distance of 5.1661(3) Å than that of 5.8317(2) Å in trans-2a. |
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Keywords: | Bisphosphine Dinuclear complex Tungsten Molybdenum Chromium |
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