Splitting the Phosphorus Bridge of 7-Phosphanorbornadiene Complexes by Fluoride Ion
作者:Carine Compain、François Mathey
DOI:10.1002/zaac.200500427
日期:2006.2
The reaction of fluorideion with 7-phosphanorbornadiene P–W(CO)5 complexes yields fluorophosphido complexes which, in turn, can attack a second molecule of 7-phosphanorbornadiene to give a fluorobiphosphine complex. The corresponding anion displays a huge P–P coupling. The structure of the anionic chromium analogue has been investigated by DFT calculations. The P–P bond is relatively short at 2.20
氟离子与 7-膦降冰片二烯 P – W (CO) 5 配合物反应生成氟磷复合物,进而可以攻击第二个 7-膦降冰片二烯分子,生成氟双膦配合物。相应的阴离子显示出巨大的 P-P 耦合。已经通过 DFT 计算研究了阴离子铬类似物的结构。P-P 键相对较短,为 2.20 A,并显示出巨大的极性,表明这是一种有趣的化学反应。当 7-磷酸降冰片二烯 P-取代基是 2-氯乙基时,氟离子的攻击之后是环化和还原性二聚反应,导致第一个已知的双膦配合物。
Simple Access to Tungsten-Stabilized Disecondary Diphosphines
Transient terminal phosphinidene complexes [RP-W(CO)(5)] dimerize in the presence of copper chloride, and the dimers react in situ with triphenylphosphine-borane to give the disecondary diphosphine complexes [RPH-PHR][W(CO)(5)](2). When R = CH2CH2Cl, a cyclization takes place to give the diphosphirane complex. A 1,2-diphospholane is obtained for R = Ph by further reaction with 1,3-dibromopropane in the presence of aqueous K2CO3.