William G. Feighery

SYNTHESIS AND CHARACTERIZATION OF SOME ALKYL(DIFERROCENYL)PHOSPHINES AND ALKYL(DIFERROCENYL)PHOSPHINE OXIDES

ABSTRACT Reaction of ferrocene with alkyldichlorophosphines (RPCl2, R=Me, Et, t-Bu) in the presence of aluminum chloride produces diferrocenyl(alkyl)phosphines (Fc2PR, (1a)–(3a), R=Me, Et, t-Bu) and diferrocenyl(alkyl) phosphine oxides Fc2P(O)R, (1b)–(3b) in low yields. Diferrocenyl(ethyl) phosphine oxide (2b) crystallizes in the P1 space group with one equivalent of water in the crystal. Compounds (1a)–(3a) are oxidized at lower potentials than the corresponding phenyl derivative, Fc2PPh. Cyclic voltammetry of (1a)–(3a) indicates that the first oxidation is irreversible. The corresponding diferrocenyl(alkyl) phosphine oxides (1b)–(3b) are more difficult to oxidize than (1a)–(3a) but show two reversible oxidations separated by 140–160 mV.

Synthesis and Electrochemistry of Alkylidynetrihydridotriruthenium Clusters with Apical pi-Substituents

The clusters, (μ-H)3Ru3(μ3-CY)(CO)9−n(PPh3)n [Y=–CH2CHCH2, n=0 (1); Y=–CH2CHCH2, n=3 (2); Y=–C6H4CH3, n=0 (3); Y=–C6H4CH3, n=3 (4)], have been synthesized in good yields and characterized by IR and NMR spectroscopy and by elemental analysis. The electrochemical properties of these clusters is also reported. These data indicate that the π-system of the apical substituent does not interact significantly with the cluster and should be available for further chemistry.

ELECTROPHILIC ADDITION TO [Rh17S2(CO)32]3−

Abstract Reactions of electrophiles with [Rh17S2(CO)32]3− produce the adducts [Rh17S2(CO)32E]2−, E = Au(PPh3), Au(PPh2Me), Ag, Rh(COD), Pt(COD)Cl, and Pd(COD)Cl, characterized by spectroscopic methods. The 13C NMR spectrum of [Rh17S2(CO)32Au(PPh3)]2− suggests that addition of the electrophile occurs at a Rh-Rh edge between the basal and internal Rh4 planes. Cyclic voltammograms for [Rh17S2(CO)32]3− and [Rh17S2(CO)32AuL]2− show several irreversible oxidation processes but two 1-electron reductions, the first of which is nearly reversible.