New chemistry based on reduction of homobinuclear bis(μ-phosphido) metal complexes
作者:Andrew Wojcicki
DOI:10.1016/s0020-1693(00)88300-0
日期:1985.5
classes of binuclear anions with CF3COOH, alkylating reagents, 1,1-diiodohydrocarbons and metal diiodo complexes have resulted in the synthesis of new binuclear and trinuclear compounds. Examples include (CO)3(H)Fe(μ-PPh2)Fe︹(CO)3(PPH2H), (CO)3Fe(μ-PPh2)(μ-C(R)O)Fe︹(CO)2(PPh2R) (R = Me, Et, n-Pr, or i-Pr), (CO)4M(μ-PPh2)2M︹(CO)3(C(R)Ome) (M = Mo or W; R = Me or Ph), (CO)2(η3−C3H5)Fe(μ−PPh2)−F︹e(CO)3(PPh2C3H5)
关于同双核双(μ-磷)金属配合物(CO)3Fe(μ-PR2)2F︹e(CO)3(R = Ph或Me),(NO)2-Fe(μ -PPh2)2F︹e(NO)2和(CO)4M(μ-PPh2)2M︹(CO)4(M = Mo或W)。已观察到两个还原途径,它们导致不同的双电子转化:(1)带有Na或LiAlH4,电子转移以产生相应的对称的二价阴离子,类型为LnM(μ-PR2)2MLn2-,而没有金属金属键;(2) M'BR'3H(M'= Li,Na或K; R'= Et或sec-Bu),氢化物转移得到LnM(μ-PR2)(μ-L)M︹Ln- 1(PR2H)−或LnM(μ-PR2)M︹Ln(PR2H)−(M = Fe,Mo或W; L = CO或NO; R = Ph或Me)。单阴离子配合物可以在-78°C下用n-BuLi脱质子化为相应的不对称双阴离子LnM(μ-PR2)(μ-L)M︹Ln-1(PR2)2-(M