6533b862fe1ef96bd12c6084

RESEARCH PRODUCT

Reactions of dirhodium(II) monometallated compounds with phosphines. Factors affecting the reactivity and the structure of the doubly-metallated compounds. Molecular structure of Rh2(O2CCH3)2[(C6H4)P(C6H5)2][(p-ClC6H3)P(p-ClC6H4)2] · (HO2CCH3)2·(C6H6), a compound with two different metallated phosphines

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Abstract Monometallated compounds of formula Rh2(O2CCH3)3[(p-XC6H3)P(p-XC6H4)2](HO2CCH3)2 (X=CH3, Cl) have been prepared in good yield. The reactions with p-substituted triarylphosphines P(p-X′C6H4)3 (X′=CH3, H, Cl) have been studied. For X=X′ and [P]/[Rh2]=1 all the resulting doubly metallated compounds Rh2(O2CCH3)2[(p- XC6H3)P(p-XC6H4)2](HO2CCH3)2 (X=CH3, Cl) have head-to-tail (H-T) structure. For [P]/[Rh2]=3 reaction progress is observed at room temperature. When X=X′ a 1:1 mixture of H-T and H-H compounds is formed for X=Cl but only the H-H compound is obtained for X=CH3. For X ≠ X′ mixtures of H-T and H-H compounds are obtained. The entering phosphine, and to a less extent the phosphine in the monometallated compound, seems to influence the rate of the process and the product distribution. The crystal structure of Rh2(O2CCH3)2[(C6H4)P(C6H5)][(p-ClC6,H3)P(p-ClC6H4)2] (HO2CCH3)2· 1 2 (C6H6) a doubly metallated compound with two different metallated phosphines in a head-to-tail configuration, is also described.