Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, E-33071 Oviedo, Spain.
Inorg Chem. 2011 Nov 7;50(21):10937-48. doi: 10.1021/ic201491v. Epub 2011 Oct 7.
The binuclear phosphine complex [Fe(2)Cp(2)(μ-CO)(2)(CO)(PH(2)Ph)] (Cp = η(5)-C(5)H(5)) reacted with the acetonitrile adduct [Fe(2)Cp(2)(μ-CO)(2)(CO)(NCMe)] in dichloromethane at 293 K to give the trinuclear hydride-phosphinidene derivative [Fe(3)Cp(3)(μ-H)(μ(3)-PPh)(CO)(4)] as a mixture of cis,anti and trans isomers (Fe-Fe = 2.7217(6) Å for the cis,anti isomer). In contrast, photochemical treatment of the phosphine complex with [Fe(2)Cp(2)(CO)(4)] gave the phosphide-bridged complex trans-[Fe(3)Cp(3)(μ-PHPh)(μ-CO)(2)(CO)(3)] as the major product, along with small amounts of the binuclear hydride-phosphide complexes [Fe(2)Cp(2)(μ-H)(μ-PHPh)(CO)(2)] (cis and trans isomers), which are more selectively prepared from [Fe(2)Cp(2)(CO)(4)] and PH(2)Ph at 388 K. The photochemical decarbonylation of either of the mentioned triiron compounds led reversibly to three different products depending on the reaction conditions: (a) the 48-electron phosphinidene cluster [Fe(3)Cp(3)(μ-H)(μ(3)-PPh)(μ-CO)(2)] (Fe-Fe = 2.592(2)-2.718(2) Å); (b) the 50-electron complex [Fe(3)Cp(3)(μ-H)(μ(3)-PPh)(μ-CO)(CO)(2)], also having carbonyl- and hydride-bridged metal-metal bonds (Fe-Fe = 2.6177(3) and 2.7611(4) Å, respectively); and (c) the 48-electron phosphide cluster [Fe(3)Cp(3)(μ-PHPh)(μ(3)-CO)(μ-CO)(2)], an isomer of the latter phosphinidene complex now having three intermetallic bonds (Fe-Fe = 2.5332(8)-2.6158(8) Å).
双核膦配合物 [Fe(2)Cp(2)(μ-CO)(2)(CO)(PH(2)Ph)]（Cp = η(5)-C(5)H(5)）与乙腈加合物 [Fe(2)Cp(2)(μ-CO)(2)(CO)(NCMe)] 在 293 K 下的二氯甲烷中反应，生成三核氢膦衍生物 [Fe(3)Cp(3)(μ-H)(μ(3)-PPh)(CO)(4)]，其为顺式，反式异构体的混合物（顺式，反式异构体的 Fe-Fe = 2.7217(6) Å）。相比之下，用 [Fe(2)Cp(2)(CO)(4)]对膦配合物进行光化学处理，得到膦桥联配合物反式-[Fe(3)Cp(3)(μ-PHPh)(μ-CO)(2)(CO)(3)]，其为主要产物，同时还有少量的双核氢膦配合物 [Fe(2)Cp(2)(μ-H)(μ-PHPh)(CO)(2)]（顺式和反式异构体），其更有选择性地由 [Fe(2)Cp(2)(CO)(4)]和 PH(2)Ph 在 388 K 下制备。所提到的三铁化合物中的任何一种的光化学脱羰反应可逆地根据反应条件产生三种不同的产物：(a) 48 电子磷化物簇 [Fe(3)Cp(3)(μ-H)(μ(3)-PPh)(μ-CO)(2)]（Fe-Fe = 2.592(2)-2.718(2) Å）；(b) 50 电子配合物 [Fe(3)Cp(3)(μ-H)(μ(3)-PPh)(μ-CO)(CO)(2)]，其具有羰基和氢化物桥接的金属-金属键（Fe-Fe = 2.6177(3) 和 2.7611(4) Å，分别）；和 (c) 48 电子膦化物簇 [Fe(3)Cp(3)(μ-PHPh)(μ(3)-CO)(μ-CO)(2)]，为后者磷化物簇的异构体，现在具有三个金属间键（Fe-Fe = 2.5332(8)-2.6158(8) Å）。
