An organometallic radical route to bis (phosphide)- and hydrido-phosphido-bridged metal-metal-bonded complexes of cyclopentadienylchromium via desulfurization of thiophosphinito ligands

Abstract

The reaction of [CpCr(CO)3]2 (1, Cp = η5C5H5) with 1 mol equiv of the tetraalkyldiphosphine disulfide R2P(S)P(S)R2 (R = Me, Et) at 60 °C for 24 h led to the isolation of the thiophosphinito complexes CpCr(CO)2(SPR2) (2a, R = Me; 2b, R = Et) as dark red solids in ca. 24% yield. Desulfurization of 2a by the organometallic radical CpCr(CO)3* (1A) gave the hydrido-phosphido-bridged complex Cp2Cr2(CO)4,(μ-H)(μ-PMe2) (3a), the bis(μ-phosphido) metal-metal doubly bonded complex Cp2Cr2(CO)2(μ-PMe2)2 (4a), and the triangulo trinuclear complex Cp3Cr3(CO)3(S)(PMe2) (5a). The solid-state structures of all of the complexes have been determined by single-crystal X-ray diffraction analysis.