Dolores Morales

Building of dithiocarbamate and dithiocarbimate ligands within a heterobimetallic core

Heterobinuclear anions [MnRe(CO)6(μ-S)(μ-SCPR3)]2− (2) undergo selective protonation and electrophilic addition of dimethylthiocarbamoyl or isothiocyanate to afford, respectively, neutral [MnRe(CO)6(μ-S2CNMe2)(μ-S2CPR3)] (3) containing μ2-(S,S′) dithiocarbamate, or anionic [MnRe(CO)6(µ-SC(S)NR′){µ-SC(H)PR3}]− (4) containing μ2-(N,S)-dithiocarbimate. The terminal sulfur in the latter can be methylated with MeI or metallated with [AuCl(p-tolyl)3] to give neutral dithiocarbimato complexes 5 or 6. The structures of 3a (R = Pri), 5a (R = Pri, R′= Et), and 5c (R = Pri, R′= Ph), have been determined by X-ray crystallography.

Hydrogen-bonded adducts between neutral molecules and [Mo(η3-methallyl)(CO)2(HOC(py)3)]+: snapshots of a deprotonation

Hydrogen-bonded adducts between the title metal alcohol complex and several neutral bases, showing different degrees of H+ transfer, display distinctive νCO bands.

A new reactivity pattern of low-valent transition-metal hydroxo complexes: straightforward synthesis of hydrosulfido complexes via reaction with carbon disulfide

A new basic transformation linking two important classes of transition metal compounds; namely, hydroxo and hydrosulfido complexes has been discovered.

A new route for the synthesis of an alkylideneamido complex

The synthesis of the new alkylideneamido complex [Re{NC(Ph)CCPh}(CO)3(bpy)] is described. Analysis of its spectroscopic and structural data reveals the absence of π-donation from the nitrogen to the metal.

Reactivity of the labile complex [MoCl(η3-allyl)(CO)2(NCMe)2] with diphosphanes

The reactions of [MoCl(η3-allyl)(CO)2(NCMe)2] (1) with variable ratios of bis(dimethylphosphanyl)methane (dmpm) or bis(diphenylphosphanyl)methane (dppm) afford different products, in which the diphosphanes are acting either as a chelate, as in [MoCl(η3-allyl)(CO)2(P–P)] (P–P = dmpm 2, dppm 6) and [Mo(NCMe)(η3-allyl)(CO)2(P–P)][{Mo(η3-allyl)(CO)2}2(μ-Cl)3] (P–P = dmpm 4, dppm 8) or as a bridge as in [{Mo(η3-allyl)(CO)2}2(μ-Cl)2(μ-P–P)] (P–P = dmpm 3, dppm 7). The analogous reaction with tetraethyldiphosphite (tedip) affords [{Mo(η3-allyl)(CO)2}2(μ-Cl)2(μ-tedip)] (5) as a single product.