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η6-triphosphabenzene, η5-triphosphacyclohexadienyl, and η5-diphosphacyclopentadienyl complexes of Group 8 and 9 metals: heterocycle transformations at the metal center

Francis, Matthew David, Holtel, Christian, Jones, Cameron and Rose, Richard Peter 2005. η6-triphosphabenzene, η5-triphosphacyclohexadienyl, and η5-diphosphacyclopentadienyl complexes of Group 8 and 9 metals: heterocycle transformations at the metal center. Organometallics 24 (17) , pp. 4216-4225. 10.1021/om0503489

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Abstract

The reactivity of a 1,3,5-triphosphabenzene, P3C3But3, 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(η5-1,3-P2C3But3)2] and an unusual heterocage complex, [(η5-1,3-P2C3But3)Fe{P2(PMe)2(CBut)3}], via phosphinidene elimination and intramolecular phosphinidene transfer reactions, respectively. The reactions of P3C3But3 or [MeP3C3But3]- with [Cp*Ru(NCMe)3][PF6] have afforded [Cp*Ru(η6-P3C3But3)][PF6] and the first example of a triphosphacyclohexadienyl−transition metal complex, [Cp*Ru{η5-(MeP)P2C3But3}]. The latter can also be prepared by treating [Cp*Ru(η6-P3C3But3)][PF6] with MeLi. Similarly, the reaction of [Cp*Ru(η6-P3C3But3)][PF6] with LiAlH4 has yielded the 2-H-triphosphacyclohexadienyl complex [Cp*Ru{η5-P3C2But2(CHBut)}]. Treatment of [Rh(COD)Cl]2 with P3C3But3 in the presence of Na[BArf4], Arf = C6H3(CF3)2-3,5, gave the complex [(COD)Rh(η6-P3C3But3)][BArf4], which when reacted with either water or ethanol afforded the 1,1-addition products [(COD)Rh{η5-[(H)(RO)P]P2C3But3}][BArf4], 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.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: American Chemical Society
ISSN: 02767333
Last Modified: 15 Dec 2017 08:36
URI: http://orca.cf.ac.uk/id/eprint/1395

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