R. B. King

Metal complexes with terminal dicyanomethylenecarbene ligands formed by chlorine migration reactions

Reactions of the 1-chloro-2,2-dicyanovinyl derivatives (NC)2CC(Cl)M(CO)3C5H5(M = Mo and W) with trivalent phosphorus and related ligands result in migration of chlorine from carbon to the transition metal to give products of the type C5H5ML2[CC(CN)2]Cl [M = Mo and W; L = Ph3P, Ph3As, Ph3Sb, (MeO)3P, (EtO)3P, and (PhO)3P] containing a terminal dicyanomethylenecarbene ligand.

Syntheses and properties of novel polyphosphines containing various combinations of primary, secondary, and tertiary phosphorus atoms

Novel polyphosphines can be prepared by the base-catalysed addition of R2P–H across the carbon–carbon double bonds of vinylphosphonate esters, followed by reduction with lithium aluminium hydride. Thus a tertiary-primary diphosphine, a tertiary-diprimary triphosphine, a tertiary-triprimary tripod tetraphosphine, and a ditertiary-diprimary linear tetraphosphine have been prepared. Similarly, the tertiary-secondary diphosphine Ph2P·CH2·CH2·PHPh can be prepared by base-catalysed addition of diphenylphosphine to isopropyl phenylvinyl-phosphinate followed by reduction. The secondary-primary diphosphine PhPH·CH2·CH2·PH2 can be prepared by the Arbusov reaction of di-isopropoxy(phenyl)phosphine with di-isopropyl 2-bromoethylphosphonate followed by reduction. The i.r., 1H n.m.r., 31P n.m.r., and mass spectra of the new compounds are discussed.

Cyclization of dicyanovinylidene with two diphenylacetylene units to form a 6,6-dicyanofulvene derivative

Reaction of (NC)2CC(Cl)Mo(CO)3C5H5 with diphenylacetylene in boiling benzene results in the cyclization of dicyanovinylidene with two diphenylacetylene units to give green 6,6-dicyano-1,2,3,4-tetraphenylfulvene.

Novel redox systems in hexamethylbenzene metal cluster compounds of niobium and tantalum

The green to brown hexamethylbenzene metal cluster compounds of stoicheiometries [(Me6C6)3M3X6]+(M = Nb and Ta; X = Cl and Br) are oxidized by a variety of oxidizing agents (e.g. CeIV, I2, N-bromosuccinimide, and air) to give salts of brown cations of the stoicheiometries [(Me6C6)3M3X6]2+(M = Nb and Ta; X = Cl and Br) isolable as their hexafluorophosphate or tetraphenylborate salts.