Cluster, phosphido

Examples of "very tnixed"-metal cluster-assisted C-heteroatom bond formation are still rare, with both literature extant examples involving coupling of bridging phosphido ligand with a C-ligand. Phosphido, hydrido, and alky tie were assembled stereospecilically to afford PPh2(( /.v-CR=CHR) (Fig. 29),-" while an unusual... 

Wiped-Film Evaporator/02 Reactivation of Catalyst. In this technology [38], spent or-ganophosphine-modified rhodium catalyst is first concentrated in a wiped-film evaporator where most of the organophosphine is removed. The rhodium concentrate is contacted with air to break down phosphido bridges in rhodium clusters. This air treated concentrate may then be used as a catalyst precursor. This procedure is suitable in circumstances where most of the aldehyde dimers, trimers and tetramers are sufficiently volatile to be removed in a wiped-film evaporator. 

Such compounds may be contacted with partially deactivated hydroformylation catalyst under non-hydroformylation conditions to effect disruption of the phosphido bridges of a rhodium cluster (Equation 2.12). After the treatment period, the catalyst solution is again suitable for hydroformylation. 

In bridged metal-metal bonded dimeric complexes, the relative importance of metal-metal and bridging ligand effects are more difficult to unravel. Dahl and his co-workers have elegantly exploited systematic crystallographic analyses to detail the stereochemical consequences of valence-electron addition or removal in dimeric metal complexes (46, 47, 65, 230) and clusters (66, 88, 204, 205, 213, 216, 222). Their experimental work has been neatly underpinned by nonparameterized approximate Hartree-Fock molecular orbital calculations (217) on the phosphido-bridged dimers [Cr2(CO)80ti-PR2)2]n"2 and [Mn2(CO)g(/i.-PR2)2]n (rt = 0, + 1, or +2) ... 

CARTY Phosphido-Bridged Iron Group Clusters... 

In this chapter we wish to focus on the synthesis, structural chemistry, and reactivity of some iron-group phosphido-bridged carbonyl clusters containing sideways-bound acetylides. The role of the PR2 group here is as a stable, unreactive, but flexible bridging coligand which facilitates exploitation of the unusual reactivity patterns for these /a2-7 2- and /Lt3-rj2-bound hydrocarbyl groups. 

A Cautionary Note on Phosphido-Bridge Reactivity. Throughout this discussion of cluster and acetylide reactivity, the phosphido... 

Phosphinoalkynes are a useful source of phosphido and acetylido groups for cluster synthesis. 

The phosphido bridge is an exceedingly versatile bridging ligand in clusters. Metal—metal bond making and... 

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