Acyliridium(III) Complexes with PCN Terdentate Ligands Including Imino- or Iminium-Acyl Moieties or Formation of Hydrido from Hydroxyl

作者：Zumeta Itziar; Mendicute Fierro Claudio; Rodriguez Dieguez Antonio; Seco Jose M; Garralda Maria A^*

来源：European Journal of Inorganic Chemistry, 2016, 2016(12): 1790-1797.

DOI：10.1002/ejic.201600056

• Iridium
• N,P ligands
• Hydrides
• Hydrogen transfer

2-Aminoalkylpyridines [H2N(CH2)(n)C5H4N] (n = 1 or 2) react with [IrHCl{(PPh2(o-C6H4CO))(2)H}] (1a) in THF to afford hydridoirida-beta-ketoimines [IrHCl{(PPh2(o-C6H4CO))(PPh2(o-C6H4CN(CH2)(n)C5H4N))H}] (2, n = 1; 3, n = 2) with intramolecular N-H center dot center dot center dot O hydrogen bonding and a dangling pyridine. In protic media 2-3 transform into [IrH(PPh2(o-C6H4CO))(PPh2(o-C6H4C=N(CH2)(n)C5H4N))] (4, n = 1; 5, n = 2) containing new terdentate PCN ligands in a facial disposition with the phosphorus atom trans to H and an iminoacyl fragment trans to the other phosphorus atom. The formation of 4-5 requires breaking of the hydrogen bond, isomerization, and dehydrochlorination of an intermediate iminium-acyl species to allow the coordination of the nitrogen atom of pyridine to iridium. The reaction of 1a with the N-substituted N-methylaminomethylpyridine allows the synthesis of [IrH(PPh2(o-C6H4CO))(PPh2(o-C6H4C=N(CH3)-CH2C5H4N))]ClO4 (6) containing a PCN ligand with an iminium-acyl moiety trans to phosphorus. The reaction of [IrH2{(PPh2(o-C6H4CO))(2)H}] (1b) with 2-(aminoalkyl)pyridines [H2N(CH2)(n)C5H4N] (n = 1 or 2) in MeOH requires the presence of KOH to afford the hydrido derivatives [IrH(PPh2(o-C6H4CO))(2)-(NH2(CH2)(n)C5H4N,kappa NH2)] (7, n = 1; 8, n = 2) were the ligands are amino-coordinated with a dangling pyridine. The reaction occurs with hydrogen evolution and transfer of hydrogen from a hydroxyl in the solvent to iridium. Single-crystal X-ray diffraction analysis was performed on 3, 4, 6, and 8.

• 出版日期2016-4