The first terminal rhenium phosphinidene complex, [Re(CO) 5 (η 1 -PN i Pr 2 )][AlCl 4 ], has been synthesized by chloride abstraction from [Re(CO) 5 {P(Cl)-(N i Pr 2 )}]. The electrophilic character of the terminal phosphinidene ligand is demonstrated by phosphine addition at the unsaturated phosphorus center and by novel reactions with azobenzene, PhNdNPh, which generate, via C-H activation and P-N and P-C bond formation, coordinated benzodiazaphosphole ligands. The cations [Re(CO) 5 P(PPh 3 )N i Pr 2 ] + and [Re(CO) 5 -{P(PhNNHC 6 H 4 )N i Pr 2 }] + have been crystallographically characterized as their AlCl 4salts. The corresponding late-metal terminal phosphinidene complexes [Co(CO) 3 -(PR 3 )(η 1 -PN i Pr 2 )][AlCl 4 ] (R ) Ph, Et) also afford coordinated benzodiazaphospholes via reaction with PhNd NPh.

The crystal structure analyses of 6 and 11 were performed by Dr. F. J. Hollander, U.C. Berkeley X-ray Crystallographic Facility, and that of 8 by Dr. W. Tótsch and J. Bularzik, K. Kourtakis, and J. Nitschke, at the same location. We thank Professor . B. Abrahamson, University of Oklahoma for a preprint. M.T. is the recipient of a Royal Fellowship of Norway. K.P.C.V. was a Camille and Henry Dreyfus Teacher-Scholar (1978-1983

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In the structure of the title compound, [Ni(C12H12N4)2(H2O)2]Cl2·2H2O, the Ni atom is linked to four N atoms and two water molecules in a distorted octahedral coordination geometry. The coordinated water molecules are engaged in hydrogen bonds with two other water molecules.