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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• 作者：Tsutomu ; Mizuta ; Satoru ; Kunikata ; Katsuhiko ; Miyoshi
• 关键词：Bisphosphine ; Dinuclear complex ; Tungsten ; Molybdenum ; Chromium
• 刊名：Journal of Organometallic Chemistry
• 出版年：2004
• 出版时间：August 15, 2004
• 年：2004
• 卷：689
• 期：16
• 页码：2624-2632
• 全文大小：411 K

文摘

A bisphosphine in which a PhPaaaPPh bond bridges 1,8-positions of naphthalene, 1,2-dihydro-1,2-diphenyl-naphtho[1,8-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(aa-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-3aaaac was converted to their respective cis isomer M(cis-1)(CO)₅. Each cis trans mixture of the mono-nuclear complexes 3aaaac was treated with the corresponding M(CO)₅(thf) to give a cis trans mixture of the respective dinuclear complexes 2aaaac. The cis isomer of the ditungsten complex 2a was isolated, and its molecular structure was confirmed by X-ray analysis, showing a shorter WaaaW distance of 5.1661(3) aaa than that of 5.8317(2) aaa in trans-2a.