Mixed-metal clusters reactions

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) ... 

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... 

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... 

Mixed-metal clusters are also accessible from Co2(CO)8. For example, the following reaction (Equation (2)) leads to a purple-black Au-Fe-Co cluster with a trigonal bipyramidal array of metals, via a long-known mixed Co-Fe red-brown colored cluster intermediate.79... 

The reaction with [Mn(CO)5]2 or [Co(CO)4]2 also led to mixed-metal clusters.962,963 Osmium-palladium mixed-metal carbonyl clusters were made using the unsaturated cluster [Os3(CO)io(/r-H)2] and the carbido cluster [Os5(/U5-C)(CO)15].964 970 Treatment of [Os3(CO)10Gu-H)2] with [Pd2(/u-dppm)2Cl2] afforded the novel high-nuclearity osmium-palladium mixed-metal carbonyl clusters [Os5Pd6(CO)13( -CO)5(/u-H)2(/u-dppm)2], [Os5Pd6(CO)13(//-CO)6(/u-dppm)2], and... 

Support for these proposals comes from several sources first, the disproportionation reactions of mixed metal clusters such as Rh2Co2(CO)j2 or Fe2Ru(CO)12 ... 

Initial addition of Co2(CO)g to Fe(CsCCsCH)(CO)2Cp occurs at the C=CH triple bond to give 156, which adds a second C02 unit to give 157 (Scheme 34). Reactions of these products with Fe2(CO)9 give mixed-metal clusters. Thus, 156... 

The development of the first alkyne silylformylation reaction was reported in 1989 by Matsuda [27]. Alkynes were treated with Me2PhSiH and Et3N with 1 mol% Rh4(CO)i2 under CO pressure to produce yS-silyl-a,/ -unsaturated aldehydes (Scheme 5.20). A second report from Ojima detailed the development of rhodium-cobalt mixed metal clusters as effective catalysts for alkyne silylformylation [28]. Shortly thereafter, Doyle reported that rhodium(II) perfluorobutyrate was a highly efficient and selective catalyst for alkyne silylformylation under remarkably mild reaction conditions (0°C, 1 atm CO) [29]. In all these reports, terminal alkynes react regiospedfically with attachment of the silane to the unsubstituted end of the alkyne. The reaction is often (but not always) stereospecific, producing the cis-product preferentially. 

Dialkylzinc derivatives are inert towards conjugated enones (e.g. 181) in hydrocarbon or ethereal solvents. The discovery that a conjugate addition can be promoted by Cu(I) salts in the presence of suitable ligands L (e.g. sulphonamide 182) opened a new route to zinc enolates (e.g. 183), and hence to the development of three-component protocols, such as the tandem 1,4-addition/aldol addition process outlined in equation 92186. If the addition of the aldehyde is carried out at —78 °C, the single adduct 184 is formed, among four possible diastereomeric products. The presence of sulphonamide is fundamental in terms of reaction kinetics its role is supposed to be in binding both Cu(I) and Zn(II) and forming a mixed metal cluster compound which acts as the true 1,4-addition catalyst. 

Several synthetic methods are now available for the preparation of mixed-metal clusters.1 However, when particular clusters are desired, two main points of concern for their synthesis often remain the availability and price of the precursors, and the yield of the reaction. Mixed-metal clusters containing ruthenium have attracted considerable interest mainly because of the variety of structural and bonding types encountered, and of their potential for homogeneous and heterogeneous catalysis.2... 

Several mixed-metal clusters containing platinum and cobalt are known and some of them have been employed as methanol homologation catalysts.1 Among them, the title compound2 was first prepared unambiguously from the reaction of dichloro[l,2-ethanediylbis(diphenylphosphine)]platinum with sodium tetracarbonylcobaltate, Na[CO(CO)4]. The compound also may be prepared by the reaction of [l,2-ethanediylbis(diphenyl-phosphine)]bis(phenylethynyl)pIatinum with Co COJg.1... 

The [Zn4(SPh)10]2- cluster anion has also been prepared by the reaction of NaSPh with ZnCl2, and H NMR studies have revealed a rapid SPh(bridgmg)-SPh(terminal) interconversion, which is thought to occur via opening of the cluster by successive breaking of two bridging Zn—S bonds.820 A rapid metal exchange reaction in the mixed-metal clusters [M4 Zn (SPh)io]2 (M = Cd, Co or Fe) and [Co4 Cd (SPh)io]2- was also detected. 

Independent discovery of the silylformylation of alkynes was reported by the Matsuda and Ojima groups. The general reaction involves addition of both CO and tertiary hydrosilane to an alkyne to yield silyl alkenals, catalyzed by rhodium or rhodium-cobalt mixed metal clusters [Eq. (46)]. 

Cleavage of the gold-methyl bond occurred in the reaction of [AuMe(PPh3)] with [H2Os3(CO)i0] (2/5), where methane elimination was accompanied by formation of the mixed-metal cluster [ H AuOs(CO)10(PPh3)]. 

The reaction of H2Os3(CO)10 with Rh(C2H4)2(MeCOCHCOMe) yields the mixed metal cluster RhOsjH2(MeCOCHCOMe)(CO)10 whose structure is shown in Figure 15. One of the acetyl-acetonate oxygen atoms, 0(3), unsymmetrically bridges Os(3) and Rh, while the other, 0(2), is coordinated only to rhodium so that this ligand can be considered as a five-electron donor.509... 

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