Carbonylmetallate anion

Fig. 60. Mixcd-melal chi.sleis from carbonylmetalate anions and dppm-slabili/cd Iriansiular clns-ters M = Pd. Pt, M = Mot i/ACjHs). W(()Tc,Hs). Mn(CO), . Co(CO). M" = MolCOld if-CsHstl. (WtCObti/ CsHs) . IMntCOtq. (CotCOtal, X = Cl. 1.

Carbocations as electron acceptors in aromatic EDA complexes 192 Bis(arene)iron(II) complexes with arene and ferrocene donors 198 Carbonylmetallate anions as electron donors in charge-transfer salts 204 Aromatic EDA complexes with osmium tetroxide 219... 

CARBONYLMETALLATE ANIONS AS ELECTRON DONORS TN CHARGE-TRANSFER SALTS... 

Thermal annihilation of carbonylmetallate anions by carbonylmetal cations... 

The carbonylmetallate anions are extremely useful organometallic reagents, particularly for the syntheses of heteropolymetallic clusters.3,4,7 However, they have rarely been isolated in the solid state and their solutions are obtained either by reduction of their dimers or by reaction of NaCsHs with the parent metal carbonyls,2 and immediately used. The first method is not very economical since the dimers are usually themselves obtained from the metallate anions. The second method has been improved as detailed below to allow the easy isolation of the pure Na[M(CO)3(//s-CsH5)] (M = Cr, Mo, W) solids as DME solvates.4 The nonsolvated Na[M(CO)3(f/5-C5H5)] salts can... 

II. Carbonylmetallate Anions as Electron Donors in Charge-Transfer Salts. 54... 

THERMAL ANNIHILATION OF CARBONYLMETALLATE ANIONS BY CARBONYLMETAL CATIONS... 

The reagent [MejSSMe] is capable of transferring a [SMe] group to metal-carbon triple bonds [see also Eq. (118)] 142). The reaction may be viewed as a direct electrophilic attack at the MC n bond. With complex 128 the dithiocarbene complex 129 is obtained [Eq. (112)]. Complex 129 reacts with nucleophiles (H , CHj", and PMe3), which add to the carbene carbon to give stable adducts [Eq. (113)]. The carbonylmetallate anions... 

Polynuclear compounds are obtained by reacting Pd(8-mq) compounds with carbonylmetallate anions. Depending upon the starting material used hetero di- or tri-metallic species are formed. 

Carbonylmetallate anions such as [CofCO) ]- can function as formal 3-electron bridges between metal atoms for example, reaction with [(PdClL)a] (L=2-[(dimethylamino)methyl]phenyl in THF gives a high (80%) yield of red crystals of [(PdL)2(iMa-Cl)(iU2-(CO)a(iM2-CO)2 ]. 

Metal acyl complexes have been prepared from sodium carbonyl-metallates.7 In the reaction of Na[Mn(CO)s] with acyl halides in dry THF, the acyl complex that is formed remains in solution and the sodium halide byproduct precipitates. The authors report that the reaction is driven mainly by the high nucleophilicity of the carbonylmetallate anion but also by the poor solubility of the sodium halide in THF, Eq. 5.4 ... 

Pfeffer and coworkers8l-83 have shown that heterobimetallic complexes containing M-M bonds can be synthesized through the reactions of carbonylmetallate anions with cyclopalladated compounds. Reaction between the palladium(II) complex (Figure 5.5) and Na[Mo(CO)3Cp] takes place only when hexane is added to a mixture of the starting materials in THF. 

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