Synthesis and Structural Characterization of Tetranuclear, Bimetallic Sulfido Nitrosyl and Carbonyl Clusters of the Type Cp₂M₂M‘₂S_3,4L_n (M = Mo, W; M‘ = Fe, Co; L = NO, CO)

Abstract

A series of new bimetallic sulfido clusters, Cp# 2M2M‘2S4(NO)2 (Cp# = C5Me2Et, C5Me5, C5H5; M = Mo, W; M‘ = Fe, Co) have been synthesized and characterized by X-ray diffraction. Two new tungsten carbonyl clusters, Cp*2W2Co2S4(CO)2 and CpEt 2W2Co2S3(CO)5, were also synthesized and the structure of the latter determined. The structural systematics are related to the redox properties and to the electronic structure of the clusters.

Catalytic functions of cubane-type M4S4 clusters

“…Curtis and coworkers studied the reactivities of Mo 2 Co 2 S 3 and Mo 2 Co 2 S 4 clusters toward desulfurization of organosulfur compounds. When [{Mo(h 5 -C 5 Me 4 Et)} 2 {Co(CO)} 2 S 4 ] was heated with excess PhSH in toluene at 150 C under CO pressure (1000 psi), PhSSPh and PhSCOPh were produced in addition to the cluster compound [{Mo(h 5 -C 5 Me 4 Et)} 2 {Co(SPh)} 2 S 4 ] (Eq 12) 89. Amount of PhSCOPh, which was produced via desulfurization of PhSH, was more than 100% per mole of the starting cluster.…”

Dianiline-1κN,2κN-bis[3,4(η5)-pentamethylcyclopentadienyl]tetra-μ3-sulfido-tetrahedro-dicopper(I)dimolybdenum(V) bis(perchlorate) aniline hemisolvate

“…There are many studies of clusters having [Mo 2 S 4 ] transition metal cores (Halbert et al 1985;Hidai et al, 2000;Ikada et al, 1998Ikada et al, , 1999Ikada et al, , 2001Kuwata & Hidai, 2001;Wei et al, 2003;Zhu et al 1990Zhu et al , 1991Takei et al, 2003;Brunner et al, 1990;Curtis et al, 1997;Kawaguchi et al, 1997;Mansour et al, 1997). Recently, we described some copper(I) complexes displaying an [( 5 -C 5 Me 5 ) 2 Mo 2 S 4 ] core for CuX (X = Cl, Br, I, SCN or CN) units (Ren et al, 2006).…”

Contents

“…The dark brown compound (HS) 2 Fe 2^3 -S)4Cr 2 cp 2 [150] exists in two isomeric forms (crystallizing in orthorhombic and monoclinic The most common cluster type in the series is Fe 2 Mo 2 , for which there are 24 known structures. In four black compounds the Fe 2 Mo 2 clusters [157,165,167,168] [159,162,163,169] [160,161,164,166,171,174], where an Fe 2 Mo 2 cluster displays a 'butterfly' conformation. In Ref.…”

“…Structural data for eight colored compounds containing Fe 2 W 2 clusters [66,162,[180][181][182][183][184][185] are given in Table 4.…”