Diphenylphosphino- or Dicyclohexylphosphino-Tethered Boryl Pincer Ligands: Syntheses of PBP Iridium(III) Complexes and Their Conversion to Iridium−Ethylene Complexes

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Two hydroborane precursors ( 1b, c ) for PBP pincer ligands bearing phenyl or cyclohexyl groups on phosphorus atoms were synthesized, and their complexation reactions with iridium were investigated. Reaction of hydroborane 1b, bearing phenyl groups, with Ir[P( p -tol) 3 ] 2 (CO)Cl afforded an 18-electron complex, [PhPBP]Ir(H)(CO)Cl ( 3b ), but reactions with other iridium(I) sources gave complicated mixtures. The characteristic IR peaks in 3b compared with the previously reported t Bu-PBP derivative 3a were discussed on the basis of theoretical calculations. Complexation of cyclohexyl-substituted hydroborane 1c with [Ir(C 2 H 4 ) 2 Cl] 2 afforded a 16-electron complex, [CyPBP]Ir(H)Cl ( 2c ). X-ray structure and computational studies on 2c revealed that the hydride ligand is close [B−H = 1.90(5) Å] to the boron atom. Reaction of 2c with LiTMP (TMP = 2,2,6,6-tetramethylpipyridide) under ethylene atmosphere gave monovalent iridium complex [CyPBP]Ir(C 2 H 4 ) ( 4c ) by a similar procedure to the previously reported [ t BuPBP] system. Exposure of a CD 2 Cl 2 solution of 2c to ethylene without additional base resulted in a quantitative formation of the intermediate [CyPBP]Ir(H)(C 2 H 4 )Cl ( 8c ), as was characterized by NMR spectroscopy. In contrast, no spectral change was observed in the same procedure using [ t BuPBP]Ir(H)Cl ( 2a ) probably due to a difference in steric bulk. The observation of 8c is a rare example of a spectroscopically identified boryl(hydrido)olefin metal complex.