Ligands migration between metals

In large part, the reactivity of a metal cluster is the same as that of the individual metal fragments. The unique features of cluster reaction chemistry involve the bridging of ligands between two or more metal atoms, ligand migration between metal atoms, and metal-metal bond cleavage and formation. 

In a series of papers entitled Structural Systematics, Orpen and co-workers used the GSD to examine a number of geometric aspects of /7-block metal complexes including torsional flexibility and conformer interconversion pathways for phosphine and diphosphine ligands, carbonyl ligand migration between metal centers (see also Figure 9,... 

A cycloaddition process between the Rh=C bond of the allenylidene derivative 38 and the C=C bond of the terminal alkyne has been evoked in the formation of the zwitterionic 71-aUyl-allenyl complexes 81 (Scheme 28), the initially formed metaUacyclobutenes 80 evolving into 81 by formation of carbene intermediate [RhCl(P/-Pr3)2(=CHCR=C=C=CPh2)] (R = Ph, p-MeC6H4, SiMe3) and subsequent migration of one of the phosphine ligands from the metal to the carbene carbon atom [205]. 

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