Abstract.Di-/x-chloro-tetrakis [2-(p-tolyl-rC2) Or-bonded ortho-metalated complexes, the dichlorobridged dimer, [Ir(ptpy)2C1]2 (I), and the facial-tris mononuclear complex, Ir(ptpy)3 (II), where ptpy is the deprotonated 2-(p-tolyl)pyridine, C iEHio N. Complex (I) has crystallographic twofold symmetry (CI atoms on the twofold axis) and (II) has crystallographic threefold symmetry (Ir atom on the threefold axis). These molecules have been synthesized and studied for their utilization in outer-sphere electrontransfer processes.
The pincer ligand dihydride complex [IrH 2 {( t Bu 2 )PCH 2 CH 2 CHCH 2 CH 2 P( t Bu 2 )}] interacts with carbon dioxide to give an isolable bicarbonate [IrH(κ 2 -O 2 COH)}{( t Bu 2 )PCH 2 CH 2 CHCH 2 CH 2 P( t Bu 2 )}] derivative and a metal hydride carbonyl compound. An intermediate metallo-formate complex can be detected by NMR spectroscopy. The reaction described is a reverse water gas shift process, CO 2 + H 2 h CO + H 2 O.
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