Synthesis, structure and reactivity of iridium complexes containing a bis-cyclometalated tridentate C^N^C ligand.

In an effort to synthesize cyclometalated iridium complexes containing a tridentate C^N^C ligand, transmetallation of [Hg(HC^N^C)Cl] (1) (H2C^N^C = 2,6-bis(4-tert-butylphenyl)pyridine) with various organoiridium starting materials has been studied. The treatment of 1 with [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene) in acetonitrile at room temperature afforded a hexanuclear Ir4Hg2 complex, [Cl(κ2C,N-HC^N^C)(cod)IrHgIr(cod)Cl2]2 (2), which features Ir-Hg-Ir and Ir-Cl-Ir bridges. Refluxing 2 with sodium acetate in tetrahydrofuran (thf) resulted in cyclometalation of the bidentate HC^N^C ligand and formation of trinuclear [(C^N^C)(cod)IrHgIr(cod)Cl2] (3).

4-Coordinated, 14-electron ruthenium(ii) chalcogenolate complexes: synthesis, electronic structure and reactions with PhICl and organic azides.

The 4-coordinated Ru chalcogenolate complexes [Ru(STipp)(PPh)] (Tipp = 2,4,6-triisopropylphenyl, 1) and [Ru(SeMes)(PPh)] (Mes = 2,4,6-trimethylphenyl, 2) have been synthesized, and their reactions with PhICl and organic azides have been studied. Complex 2 synthesized from [Ru(PPh)Cl] and NaSeMes displays a seesaw structure with P-Ru-P and Se-Ru-Se bond angles of 103.43(13) and 145.