NEW TRANSITION METAL COMPLEXES & COMPOUNDS W/NITRILE & PHOSPHINE LIGANDS

溶剂化单核和双核配合物与新的 具有不寻常的空间和/或电子的膦配体 性质和与氰化物或聚腈受体分子将是 研究了 先前未知的溶剂化阳离子[M2（MeCN）10]4+ （M = Re，Rh）最近在我们的实验室制备了这些 应用;战略概述了合成的W，O 和Ir类似物。 有机富瓦烯供体将共价地 通过中间的磷原子连接到金属上， 具有四硫富瓦烯基团的新膦配体。 在 平面正方形Rh（I）分子 由[Rh 2（MeCN）10][BF 4]4制备的[Rh{Ph 2 P（Me 2-TTF）PPh 2}2][BF 4]是 在固态下相互作用Me 2 TTF重叠 膦上的基团。 合成策略也概述了 金属VII的低价二元和三元氰化物， MnII、MoII和ReII及其各种组合，以 金属乙腈阳离子。 新型金属-金属键合阴离子[Mo 2 [（CN）8]4-已通过该方法制备;产物具有 CN-桥获得较低的CN-/Mo比。 特别是， Bu 4 N +CN-与[M2（MeCN）10]4+（M = Mo、Re、Rh）的反应，以及 [M（MeCN）6]2+（M = V，Mn）将被强调。 新的反应 多氰化物阴离子与溶剂化的金属阳离子以产生混合金属 氰化物也在计划中。 MALDI-和FAB-MS已被用于 以确定模型化合物的分子量。

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.