Synthesis and Reactivities of Cubane-Type Sulfido Clusters Containing Noble Metals

Abstract

Cubane-type sulfido clusters containing noble metals are newcomers compared with the corresponding clusters of the first transition series metals and molybdenum, which have been extensively studied in relation to metalloenzymes and industrial hydrodesulfurization catalysts. This Account reviews the recent progress in studies on the synthesis and reactivities of these noble metal cubane-type clusters. One of the goals in this new area lies in development of the unique catalysis of the noble metals embedded in the robust and redox-active cubane-type cores. Rational synthetic approaches indispensable to the preparation of such effective cluster catalysts are discussed to a significant extent.

A New Series of Homologous Cluster Complexes [Mo3(M'EPh3)Q4Cl4(H2O)5] (M' = Ni, Pd; E = P, As, Sb; Q = S, Se)

“…[1] The bioinorganic significance of metal sulfide clusters is well known, and it has been put forward that the Mo 3 MЈS 4 (MЈ = Co, Ni) clusters in particular can constitute molecular models for the active sites of the industrial heterogeneous Co/MoS 2 or Ni/MoS 2 catalysts. [2] The Mo 3 PdS 4 4+ clusters catalyze nucleophilic addition to alkynes [3] and [Mo 3 NiS 4 (H 2 O) 10 ] 4+ has proved to be efficient in various heterogeneous catalytic processes. [4,5] Recently it was found that the heterometal in M 3 MЈS 4 4+ clusters (M = Mo, W; heterometal (MЈ) = Ni, Pd) stabilize very labile molecules of P(OH) 3 , RP(OH) 2 (R = H, Ph) and Ph 2 P(OH) by coordination at phosphorus [6][7][8] .…”

“…[2] The Mo 3 PdS 4 4+ clusters catalyze nucleophilic addition to alkynes [3] and [Mo 3 NiS 4 (H 2 O) 10 ] 4+ has proved to be efficient in various heterogeneous catalytic processes. [4,5] Recently it was found that the heterometal in M 3 MЈS 4 4+ clusters (M = Mo, W; heterometal (MЈ) = Ni, Pd) stabilize very labile molecules of P(OH) 3 , RP(OH) 2 (R = H, Ph) and Ph 2 P(OH) by coordination at phosphorus [6][7][8] . Nonlinear optical properties of [M 3 (CuX)Q 4 (dmpe) 3 X 3 ]PF 6 (M = Mo, W; X = Cl, Br; Q = S, Se) were also studied.…”

“…[4,5] Recently it was found that the heterometal in M 3 MЈS 4 4+ clusters (M = Mo, W; heterometal (MЈ) = Ni, Pd) stabilize very labile molecules of P(OH) 3 , RP(OH) 2 (R = H, Ph) and Ph 2 P(OH) by coordination at phosphorus [6][7][8] . Nonlinear optical properties of [M 3 (CuX)Q 4 (dmpe) 3 X 3 ]PF 6 (M = Mo, W; X = Cl, Br; Q = S, Se) were also studied. [9] A rational synthesis of these clusters is based on an addition of a heterometal in a low oxidation state (or even MЈ 0 ) to the trinuclear complexes with the M 3 Q 4 4+ cores.…”

“…[10] However, ligand substitution has not been widely used so far for the isolation of the heterometallic clusters from aqueous solutions. 3+ [16] and [Mo 3 (Pd(dppe))S 4 (dppe) 3 Cl 3 ]Cl [18] 5-. [19,20] This scarcity may be attributed to enhanced lability of the cluster cores upon changing the coordination environment, which leads to the loss of the heterometal.…”

A Novel Route to Multinuclear d8 Metal−Chalcogen Compounds with Nuclearity Control

“…[3] Here we report a novel synthetic route based on the behavior of [L 2 Pt(µ-S) 2 PtL 2 ] compounds as metalloligands, which leads to multinuclear aggregates containing a {Pt 2 S 2 } n core. The synthetic strategy allows control of the nuclearity of the cluster and can be extended to other metals with square-planar coordination.…”