The preparation of [M2Cp2(CO)4(n-T]2-PE) (E = as or Sb), the first complexes with naked heterodiatomic Group 15 ligands, and of their adducts with W(CO)5

John E. Davies, Martin J. Mays, Paul R. Raithby, Gregory P. Shields, Peter K. Tompkin, Anthony D. Woods

Research output: Contribution to journalArticle

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Abstract

Addition of one equivalent of the Group 15 trichlorides EC13 (E = P, As, or Sb) to the phosphido-bridged dimetallic anions [M2Cp2(CO)4(u-PH2)]- (M = Mo or \V) afforded moderate yields of the complexes [M2Cp2(CO)4(n-n2-PE)], which feature a pseudo-tetrahedral M2PE core. Treatment of the new complexes with [W(CO)5(THF)] led to preferential co-ordination of this Lewis acid to the phosphorus atom. The additional co-ordination of a W(CO)5 fragment to the As atom in [M2Cp2(CO)4(u-n2-PAs)] to give a 2:1 adduct is reversible at room temperature on dissolution in solvents such as CH2C12 and THF; similar co-ordination to the Sb atom in [M2Cp2(CO)4(u-r|:-PSb)] is not observed. The crystal structures of the 1:1 adducts and of one 2:1 adduct have been determined. The P-As distances in [W2Cp2(CO)4{uV-AsPW(CO)5}] (2.217(5) A) and that in [Mo2Cp2(CO)4(u-ii2-AsP{W(CO)5}2)], in which the As and P atoms are disordered (2.223(3) A), are intermediate between the P-P and As-As distances in homodiatomic E2 complexes. Similarly, the P-Sb distances in the two crystallographically independent molecules of [Mo2Cp2(CO)4{u-n2-SbP\V(CO)5}] (2.401(2), 2.410(2) A) are intermediate in length between the P-P and Sb-Sb distances in related homodiatomic E2 complexes.

Original languageEnglish
Pages (from-to)1925-1930
Number of pages6
JournalJournal of the Chemical Society, Dalton Transactions
Issue number12
DOIs
Publication statusPublished - 2000

ASJC Scopus subject areas

  • Chemistry(all)

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