ATMENDE CLUSTER: ADDITION UND ELIMINIERUNG ALS ELEMENTARSCHRITTE DER LIGANDENSUBSTITUTION AN (μ3-RP)Fe3(CO)10

Article abstract of DOI:10.1016/0022-328X(85)88055-4

The closed tetrahedral clusters RPFe3(CO)_(10-n)L_n (1) (R = alkyl, aryl; L = phosphite, isonitrile; n = 0, 1, 2,) add ligands L by opening of metal-metal bonds in a stepwise manner to give RPFe3(CO)_(10-n)L_(n+1) (2) and RPFe3(CO)_(10-n)L_(n+2) (3) respectively.By stepwise elimination of L the closed tetrahedral clusters 1 are obtained from the M-M bond-opened species 3 and 2, respectively.Elimination of CO from 3 or 2 yields substituted clusters of type 2 or 1, respectively, again in a stepwise manner.This reaction sequence, documented by several examples, demonstrates that clusters behave like breathing objects which reversibly add substrates to their inner surface and expire them under reformation of metal-metal bonds.Hence, ligand substitution does not occur as a dissociatively initiated process on the outer surface of a cluster but involves addition-elimination sequences on the inner surface of the polyhedron.