Rh₄(µ₄-PPh)₂(cyclo-octa-1,5-diene)₄. A doubly co-ordinatively unsaturated phosphinindene-bridged cluster without carbonyl ligands

Abstract

The n e w cluster R h 4 ( p 4 -P P h ) 2 ( ~~d ) 4(cod = cyclo-octa-I ,5-diene) has been prepared by the reaction of Li2PPh with R h 2 ( p -C 1 ) 2 ( ~~d ) 2 or the reaction of Rh2(p-PPh2) (p-CI) with LiCBHEt,] and has been spectroscopically and structurally characterized.

Phosphinidene- and Phosphido-Bridged Complexes from a η2-Arylthioxophosphane Cyclopentadienylchromium Complex

“…Complexes 5 and 6 contain one and two μ 3 -phosphinidene ligands, respectively, at the corners of cubanes. There are several instances of the occurrence of μ 3 -phosphinidene in clusters of Fe 5 and Ru, 6b,c but only one reported example of a μ 3 -phosphinidene cubane, viz. (Cp‘Mo) 2 (Co(CO) 2 S 3 (PPh) .…”

“…The majority of these μ 3 complexes contain the M 3 (CO) n ( n = 6, 8, 9) cluster moieties of group 8 metals (M = Fe, M = Ru, Os 6a,b ), with some containing bis μ 3 or μ 4 ligands, e.g. Fe 3 (CO) 9 (μ 3 -PR) 2 ,5h Fe 4 (CO) 11 (μ 3 -PR) 2 ,5i (cod) 4 Rh 4 (μ 4 -PPh) 2 ,6d and Ru 4 (CO) 10 ( μ -CO)( μ 4 −PPh) 2 8a. Heterometallic examples include MCo 2 ( μ 3 -PCy)(CO) 9 (M = Fe, Ru),7a MnFeCo(CO) 10 ( μ -PR),7b Cp/Cp*WRu n (CO) 10 ( μ 3 -H)( μ 3 -PPh) ( n = 2, 3), 7c and Ru 3 (CO) 9 ( μ -Au(PMe 2 Ph))( μ -H)( μ 3 -PPh) 7d.…”

“…The main synthetic pathways to these complexes are represented by (i) the reaction of M 3 (CO) 12 (e.g. for M = Fe, Ru) with RP(S)Cl 2 ,5a [RP(S)S] 2 ,5a or H 2 PPh,6a (ii) the reaction of Na 2 [Fe(CO) 4 ] with RP(S)Cl 2 ,5b and (iii) P−C(Ph) bond activation of the μ-phosphido complex HM 3 (CO) 10 (μ-PPh 2 ) (M = Ru, Os) 6c. The single μ 3 -phosphinidene cubane reported to date is the cluster (Cp‘Mo) 2 Co(CO) 2 S 3 (PPh), derived from the reaction of (Cp‘Mo) 2 (Co(CO) 2 ) 2 S 3 with H 2 PPh .…”