165134-38-3Relevant academic research and scientific papers
Reactions of the phosphinidene-bridged complexes [Fe2(η 5-C5H5)2(μ-PR)(μ-CO)(CO) 2] (R = Cy, Ph) with electrophiles based on p-block elements
Alvarez, M. Angeles,Garcia, M. Esther,Gonzalez, Rocio,Ruiz, Miguel A.
, p. 14498 - 14513 (2012)
The title complexes reacted readily with the methylating agents MeI and CF3SO3Me, chalcogens (O2, S8) and borane adducts BH3·L (L = THF, NtBu3, PPh3) to initially give the corresponding neutral or cationic derivatives of the type [Fe2Cp2{μ-P(E)R}(μ-CO)(CO) 2]n (Cp = η5-C5H5; n = 0, E = O, S, BH3; n = +1, E = Me), which could be further functionalized through additional reactions. Thus, the oxophosphinidene complex [Fe2Cp2{μ-P(O)Cy}(μ-CO)(CO)2] could be protonated or alkylated with HBF4·OEt2 or CF 3SO3Me, to give the complexes [Fe2Cp 2{μ-P(OR′)Cy}(μ-CO)(CO)2]+ (R′ = H, Me) respectively, while the photochemical treatment of compounds [Fe2Cp2{μ-P(BH3)R}(μ-CO)(CO) 2] gave the dicarbonyl derivatives [Fe2Cp 2{μ-κ1:κ1,η2- P(BH3)R}(μ-CO)(CO)], with a phosphinidene-borane ligand displaying coordination of a B-H bond to one of the iron atoms in a side-on fashion (Fe-H = 1.78(4) A, Fe-B = 2.351(5) A for the PCy compound). The title complexes also reacted readily with 3,5-di-tert-butyl-o-benzoquinone or benzyl azide. The first reaction gave the phosphonite complex [Fe2Cp 2(μ-CO)2(CO){P(O2C6H 2tBu2)R}], while the second reaction yielded initially the corresponding 1:1 adducts [Fe2Cp2{μ- P(N3CH2Ph)R}(μ-CO)(CO)2], with a P:P-bound phosphatriazadiene ligand. The PCy compound underwent clean denitrogenation in toluene at 368 K to give the iminophosphinidene complex [Fe2Cp 2{μ-P(NCH2Ph)Cy}(μ-CO)(CO)2], which in turn could be protonated selectively with [NH4]PF6 at the P-bound nitrogen atom, to yield the aminophosphide derivative [Fe 2Cp2{μ-P(NHCH2Ph)Cy}(μ-CO)(CO) 2]PF6 (Fe-Fe = 2.6362(8) A). Denitrogenation could be also induced photochemically on the phosphatriazadiene complex, but this also caused fragmentation and recombination of different bonds to give the trinuclear compound [Fe3Cp3(μ3-PCy){μ- κ1:κ1-C(O)(NHCH2Ph)}(μ-CO) 2], having phosphinidene and C:O-bound aminoacyl ligands bridging the metal atoms.
