Syntheses and Structures of Mixed-Metal Sulfido Clusters Containing Trimetallic M₂M‘S₄(M = Mo, W; M‘ = Pd, Pt) and Tetrametallic Cubane-Type Mo₂Pd₂S₄Cores

Abstract

The reaction of the sulfido-bridged dimolybdenum or ditungsten complex [M 2 S 2 (µ 2 -S) 2 (S 2 CNEt 2 ) 2 ] (M ) Mo (1a), W) with an equimolar amount of [M′(PPh 3 ) 4 ] (M′ ) Pd, Pt) gave a series of mixed-metal sulfido clusters with a trimetallic M 2 M′ core [M′(PPh 3 )(µ 2 -S) 2 {M(S 2 CNEt 2 )} 2 (µ 2 -S) 2 ]. The X-ray diffraction study for [Pt(PPh 3 )(µ 2 -S) 2 {W(S 2 CNEt 2 )} 2 (µ 2 -S) 2 ] (3b) has disclosed the presence of a novel triangular framework, for which the two Pt-W edges are each bridged by one µ 2 -S ligand and the remaining W-W edge is supported by two µ 2 -S ligands. Cluster 3b crystallized in the monoclinic system, space group C2/c with a ) 13.718(3) Å, b ) 12.795(2) Å, c ) 43.798(2) Å, β ) 95.24(1)°, and Z ) 8. Refinement by full-matrix least-squares techniques gave final residuals R ) 0.052 and R w ) 0.038. Treatment of [Pd(PPh 3 )(µ 2 -S) 2 {Mo(S 2 CNEt 2 )} 2 (µ 2 -S) 2 ] with an additional amount of [Pd(PPh 3 ) 4 ] resulted in the formation of the cubane-type mixed-metal sulfido cluster [{Pd(PPh 3 )} 2 {Mo(S 2 -CNEt 2 )} 2 (µ 3 -S) 4 ], which was also obtained straightforwardly from the reaction of 1a with 2 equiv of [Pd(PPh 3 ) 4 ].

Stepwise addition of CuBr at [(dtc)2Mo2(S)2(μ-S)2] (dtc=diethyldithiocarbamate): syntheses and crystal structures of two Mo/Cu/S clusters [(dtc)2Mo2(μ3-S)(μ-S)3(CuBr)] and [(dtc)2Mo2(μ3-S)4(CuBr)2]

“…In the chemistry of thiometallates, some reactions could be controlled by molar ratios of the reactants. One successful example is the reactions of [(dtc) 2 Mo 2 S 2 (m-S) 2 ] with one or two equivalents of [Pd(PPh 3 ) 4 ], from which the trinuclear cluster [(dtc) 2 Mo 2 (m 3 -S)(m-S) 3 Pd(PPh 3 )] and the tetranuclear cluster [(dtc) 2 Mo 2 (m 3 -S) 4 Pd 2 (PPh 3 ) 2 ] are isolated [25].…”

“…Another interesting precursor [(dtc) 2 Mo 2 (S) 2 (m-S) 2 ] [42] has been adopted to react with noble metal complexes to yield a set of the incomplete Mo 2 M?S 4 cubane-like clusters and the complete Mo 2 M ? 2 S 4 cubane-like clusters (M?0/Pt, Pd, Ir) [4,25,29]. However, reactions of these sulfidobridged dinuclear complexes with Cu(I) are less explored [10,11].…”

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).…”

Synthesis, structure and photoluminescence of a novel palladium(I) compound: [Pd3(μ3-Cl)2(dppp)3][Pd2(μ2-Cl)3(PPh3)2](PPh3)2

“…The molecular structure demonstrates that each palladium(I) center of the anionic portion may be surprisingly viewed as distorted tetrahedral arrangement if the metal-metal bond is ignored, whereas most of Pd(I) dimmers previously reported have trigonal geometries if the metal-metal bond is excluded or very distorted square-planar geometries if it is included [22][23][24]. As far as we know, the first example of Pd(I) in a tetrahedral manner in the literature was ever reported by Ikada and co-workers [7]. Therefore, this is the second case of the tetrahedral coordination environment in palladium(I) chemistry and the first example of palladium(I) dimmer with three bridging halogen atoms.…”

“…However, a common structural feature of the majority of these complexes is that the center of palladium(I) generally adopts square-planar (or distorted square-planar) and trigonal coordination geometries. The only example of palladium(I) in a tetrahedral manner was ever reported by Ikada and co-workers [7]. On the other hand, most of the studies carried out on trinuclear palladium clusters have focused on Pd nþ 3 (n = 0, 1, 2) species [8][9][10][11][12][13] and there are rare Pd 3þ 3 clusters reported.…”