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RESEARCH PRODUCT

Synthesis, Molecular Structure, and Reactivity of Rhodium(I) Complexes with Diazoalkanes and Related Substrates as Ligands

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A series of (diazoalkane)rhodium(I) compounds of the general composition trans-[RhCl(N2CRR‘)(PiPr3)2] with R = R‘ = Ph, p-C6H4Me, p-C6H4Cl and R = Ph, R‘ = p-C6H4Me, o-C6H4Me, CH3, CH2Ph, CF3 has been prepared from the dimer [RhCl(PiPr3)2]2 (1) and the diazoalkane. This preparative route has also been extended to complexes in which the N2C unit(s) of 1,4-C6H4{C(Ph)N2}2, 9-diazofluorene, 9,10-anthraquinone-9-diazide, and 3-methyl-1,4-naphthoquinone-1-diazide is (are) linked to a 14-electron [RhCl(PiPr3)2] fragment. While C(CO2Et)2N2 behaves as expected and affords upon treatment with 1 the complex trans-[RhCl{N2C(CO2Et)2}(PiPr3)2), CH(CO2Et)N2 reacts with the same starting material to give the dinitrogen derivative trans-[RhCl(N2)(PiPr3)2] (12). The reactions of trans-[RhCl(C2H4)(PiPr3)2] (2) with both N2CC4Cl4 and N2CC4Ph4 afford trans-[RhCl(N2CC4X4)(PiPr3)2] (X = Cl, Ph), and the same type of ligand exchange takes place by treatment of trans-[RhCl(C2H4)(SbiPr3)2] with N2CC4Cl4. The reactions of trans-[Rh...