Reactions of solvated mononuclear and dinuclear complexes with new phosphine ligands possessing unusual steric and/or electronic properties and with cyanide or polynitrile acceptor molecules will be investigated. The previously unknown solvated cations [M2(MeCN)10]4+ (M = Re, Rh) were recently prepared in our laboratories for these applications; strategies are outlined for the syntheses of the W, Os and Ir analogues. Organic fulvalene donors will be covalently attached to metals through an intervening phosphorus atom by the use of new phosphine ligands with tetrathiafulvalene groups. In preliminary work, the square planar Rh(I) molecule [Rh{Ph2P(Me2-TTF)PPh2}2][BF4] prepared from [Rh2(MeCN)10][BF4]4 was seen to interact in the solid state through ?-overlap of the Me2TTF groups on the phosphine. Synthetic strategies are also outlined for low-valent binary and ternary cyanide compounds for the metals VII, MnII, MoII and ReII and various combinations thereof, beginning with metal acetonitrile cations. The new metal-metal bonded anion [Mo2 (CN)8]4- has been prepared by this method; products possessing CN-bridges are obtained for lower CN-/Mo ratios. In particular, reactions of Bu4N+CN- with [M2(MeCN)10]4+ (M = Mo, Re, Rh) and [M(MeCN)6]2+ (M = V, Mn) will be emphasized. Reactions of new polycyanide anions with solvated metal cations to produce mixed-metal cyanide compounds are also planned. MALDI- and FAB-MS have been used to determine molecular weights for model compounds.
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