864069-75-0Relevant academic research and scientific papers
η6-Triphosphabenzene, η 5-triphosphacyclohexadienyl, and η 5-diphosphacyclopentadienyl complexes of group 8 and 9 metals: Heterocycle transformations at the metal center
Francis, Matthew D.,Holtel, Christian,Jones, Cameron,Rose, Richard P.
, p. 4216 - 4225 (2008/10/09)
The reactivity of a 1,3,5-triphosphabenzene, P3C 3But3, and a triphosphacyclohexadienyl anion, [MeP3C3But3]-, toward a range of group 8 and 9 halide complexes has been investigated. The anion reacts with FeCl2 to give the known tetraphosphaferrocene [Fe(η 5-l,3-P2C3But3) 2] and an unusual heterocage complex, [η5-1,3P 2C3But3)Fe{P2(PMe) 2(CBut)3}], via phosphinidene elimination and intramolecular phosphinidene transfer reactions, re-spectively. The reactions of P3C3But3 or [MeP 3C3But3]- with [Cp*Ru(NCMe)3] [PF6] have afforded [Cp*Ru(η6-P3C3But 3)] [PFe] and the first example of a triphosphacyclohexadienyl-transition metal complex, [Cp*Ru{η 5-(MeP)P2C3But3}]. The latter can also be prepared by treating [Cp*Ru(η6-P 3C3But3)] [PF6] with MeLi. Similarly, the reaction of [η*Ru(η6-P 3C3-But3)][PF6] with LiA1H4 has yielded the 2-H-triphosphacyclohexadienyl complex [Cp*Ru-{η5-P3C2But 2(CHBut)}]. Treatment of [Rh(COD)Cl]2 with PC3But3 in the presence of Na[BAr f4], Arf = C6H3(CF 3)2-3,5, gave the complex [(COD)Rh(η 6-P3C3But3)] [BAr f4], which when reacted with either water or ethanol afforded the 1,1-addition products [(COD)Rh{η5-[(H)-(RO)P]P 2C3But3}][BArf 4], R = H or Et. The mechanisms of the various heterocycle transformation reactions are discussed, and the X-ray crystal structures of all new complexes are reported.
