Clusters mixed metal

As in previous accounts, the chemistry of clusters containing metals from more than one group of the Periodic Table is considered in this section, complexes being arranged in order of lowest Periodic Group number. 

A review of very-mixed -metal carbonyl clusters, covering complexes containing transition metals separated by at least three d-block groups has been published, and Adams has briefly reviewed the reactivity of segregated bimetallic clusters and their role in catalysis.  

2 Group 6. - 15.2.1 Mo, W Fe. A series of crown ethers containing from one to three tetrahedral [M2Fe( i3-S)] (M = Mo units have been reported from the self-assembly cyclisation of polyether chain-bridged precursors electrochemical data were also presented. 

Phosphine-stabilised cubane clusters containing reduced [MoFe3S4] cores have been prepared from treatment of appropriate oxidised precursors with Na(BPh4) in the presence of PR3 (R = Bu, PP) complexes include single, double and tetracubane clusters.  

8)2(00)10] with [Mo(C = CPh)(CO)3Cp] afforded the spiked-triangular linked cluster [Mo2WFe2( i3-S)2( i-CCPh)2(ii-0)(0)(CO)9Cp2] (150), the redox properties of which have been discussed.  

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The method is clearly of potential use in preparing mixed metal clusters, e.g. (Co -t- Ni) or (Co -t-Fe), and can be extended to prepare more complicated cluster arrays as depicted below, the subrogated B atom being indicated as a shaded circle in (92). 

Many novel cluster compounds have now been prepared in this way, including mixed metal clusters. Further routes involve the oxidative fusion of dicarbon metallacarborane anions to give dimetal tetracarbon clusters such as (103) and (104) O (jjg insertion of isonitriles into inetallaborane clusters to give monocarbon meiallacarboranes such as (105) and the reaction of small ii/t/o-carboranes with alane adducts such as Et3NAlH3 to give the commo species (106) ... 

Synthesis, molecular dynamics and reactivity of mixed-metal clusters. G. L. Geoffrey, Acc. Chem. Res., 1980,13,469-476 (29). 

These methods may be used to prepare mixed metal clusters. Simultaneous codeposition of Ag and Cu vapors in Ar at 10-12 K yields a mixture including atomic Ag and Cu, dimers Ag, and Cu, together with AgCu. At 77 K, CuAg4 and Cu,Ag3 clusters occur . The amount of AgCu can be increased by photoexcitation with 305 nm Ag or Cu atomic radiation. The trimer AuAgCu is produced when a mixture of Au, Ag and Cu vapors is condensed at 77 K. 

Ligand activation and transformation at heterometallic clusters have been reviewed, but few examples of very mixed -metal clusters effecting these... 

The premise of this review is that synthetic procedures for very mixed"-metal clusters are comparatively well understood, but that reactivity and physical properties are less well studied. Metal core transformations (modifications of a preexisting cluster) fall into both the synthesis and reactivity categories. A summary is presented here, but as they have been reviewed elsewhere (see Refs. 4, 107-109), the account below is necessarily brief. Section lI.E. 1. considers core transformations where the cluster core nuclearity is pre.served, whereas Section 11.E.2. summarizes reactions involving a change in core size. 

Efficient routes into very mixed -metal clusters by metal exchange reactions have been developed, principally by Vahrenkamp and co-workers. Metal exchange... 

Fi(i. 39. Mixed-metal cluster formation employing IMtAsMesKC Otd f -CsHf)]. 

Research into cluster catalysis has been driven by both intrinsic interest and utilitarian potential. Catalysis involving "very mixed -metal clusters is of particular interest as many established heterogeneously catalyzed processes couple mid and late transition metals (e.g., hydrodesulfurization and petroleum reforming). Attempts to model catalytic transformations arc summarized in Section II.F.I., while the use of "very mixed -metal clusters as homogeneous and heterogeneous catalysis precursors are discussed in Sections I1.F.2. and I1.F.3., respectively. The general area of mixed-metal cluster catalysis has been summarized in excellent reviews by Braunstein and Rose while the tabulated results are intended to be comprehensive in scope, the discussion below focuses on the more recent results. 

Reactivity studies of organic ligands with mixed-metal clusters have been utilized in an attempt to shed light on the fundamental steps that occur in heterogeneous catalysis (Table VIII), although the correspondence between cluster chemistry and surface-adsorbate interactions is often poor. While some of these studies have been mentioned in Section ll.D., it is useful to revisit them in the context of the catalytic process for which they are models. Shapley and co-workers have examined the solution chemistry of tungsten-iridium clusters in an effort to understand hydrogenolysis of butane. The reaction of excess diphenylacetylene with... 

Homogeneous catalysis by transition metal clusters has been reviewed from the perspective of the specific transformations.Examples of very mixed-metal clusters catalyzing processes homogeneously are collected in Table IX. As is generally the case with homogeneous catalysis, the catalytic precursor is well defined, but the nature of the active catalyst is unclear. 

The focus of research on very mixed"-metal clusters has been on their synthesis and structure, and the limited physical measurements of these clusters have thus far been largely restricted to fluxionality and electrochemical investigations. Studies of ligand fluxionality are summarized in Section 111.A. and reports of electrochemical investigations are reviewed in Section Ill.B. The few reports of the magnetic behavior of these clusters are discussed in Section lll.C. 1., and theoretical studies are summarized in Section I1I.C.2. 

Table XI summarizes reports of ligand fluxionality at "very mixed -metal clusters. A number of studies (c.g.. Refs. 28, 8I, 116, 213, 214) have reported that both metal-localized and global carbonyl fluxionality occur but give little mechanistic detail. The following discussion focuses on the examples for which detailed studies have been undertaken and/or those for which mechanistic speculation is available.

The electrochemical behavior of heterometallic clusters has been reviewed clsewbcre."" The interest in examining clusters stems from their potential to act as "electron sinks " in principle, an aggregate of several metal atoms may be capable of multiple redox state changes. The incorporation of heterometals provides the opportunity to tune the electrochemical response, effects which should be maximized in very mixed"-metal clusters. Few very mixed -metal clusters have been subjected to detailed electrochemical studies the majority of reports deal with cyclic voltammetry only. Table XII contains a summary of electrochemical investigations of "very mixed"-metal clusters. 

The electronic, optical, and magnetic properties of metal clusters are of great current interest, but these properties have been little studied with very mixed -metal clusters. This is to some extent a reflection of the difficulty of preparing high-nuclearity examples many of these interesting properties become important upon increasing cluster size. The limited magnetic studies to date are... 

The limited magnetic measurements of very mixed -metal clusters are summarized in Table XIII. The magnetic behavior of some anti-ferromagnetic very mixed -metal carbonyl clusters (Fig. 82) has been studied by Pasynskii and eo-workers. Temperature dependences of the magnetic susceptibilities of Cr2Co(/t3-S)3(/i-SBu )(CO)2() -C3H4R)2l (R = H. Me) have been determined us-... 

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