Hydrogen and oxygen activation by an iridium precursor containing the 4,5-bis(diphenylthiophosphinoyl)-1,2,3-triazolate ligandElectronic supplementary information (ESI) available: Selected 1H-and 31P{1H}-NMR spectra of 1-5, crystal X-ray structure data of 1, 2, 4, 5a, and 5b, and computational details of complexes 1, 2, 3 and 4. CCDC 1061702-1061706. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5ra07698f

• Main Authors: Hernández-Juárez, M, Toscano, R. A, Cortés-Guzmán, F, Zúñiga-Villarreal, N
• Format: Article
• Language: English
• ISSN: 2046-2069
• DOI: 10.1039/c5ra07698f

The novel mononuclear complex [Ir(κ 2 - S , N -(4,5-(P(S)Ph 2 ) 2 Tz))(coe) 2 ] was prepared starting from the dimer [Ir(coe) 2 (μ-Cl)] 2 (coe = cyclooctene) and potassium 4,5-bis(diphenylthiophosphinoyl)-1,2,3-triazolate, K[4,5-(P(S)Ph 2 ) 2 Tz]. Reaction of [Ir(κ 2 - S , N -(4,5-(P(S)Ph 2 ) 2 Tz))(coe) 2 ] with two equivalents of PPh 3 led to complex [Ir(κ 2 - S , N -(4,5-(P(S)Ph 2 ) 2 Tz))(PPh 3 ) 2 ]; which, upon exposure to atmospheric air at room temperature, fixed molecular oxygen to produce complex [Ir(κ 2 - S , N -(4,5-(P(S)Ph 2 ) 2 Tz))(PPh 3 ) 2 O 2 ]. Molecular hydrogen also added oxidatively to complex [Ir(κ 2 - S , N -(4,5-(P(S)Ph 2 ) 2 Tz))(PPh 3 ) 2 ] to form the Ir( iii ) dihydride complex [Ir(κ 2 - S , N -(4,5-(P(S)Ph 2 ) 2 Tz))(PPh 3 ) 2 (H) 2 ]. Carbon-hydrogen bond activation was effected when complex [Ir(κ 2 - S , N -(4,5-(P(S)Ph 2 ) 2 Tz))(coe) 2 ] was made to react with triphenylphosphite to give the ortho -metallated complex [Ir(κ 2 - S , N -(4,5-(P(S)Ph 2 ) 2 Tz))(P(OC 6 H 4 )(OPh) 2 )(P(P(OPh) 3 )(H)]. The new compounds were characterized by spectroscopic methods and, excepting for [Ir(κ 2 - S , N -(4,5-(P(S)Ph 2 ) 2 Tz))(PPh 3 ) 2 ], by single crystal X-ray analysis. Oxygen and hydrogen activation by the diphosphane complex [Ir(κ 2 - S , N -(4,5-(P(S)Ph 2 ) 2 Tz))(PPh 3 ) 2 ] compared with the inertness of the diolefin complex [Ir(κ 2 - S , N -(4,5-(P(S)Ph 2 ) 2 Tz))(coe) 2 ] to such processes was assessed by means of a DFT-QTAIM analysis. Complex [Ir(κ 2 - S , N -(4,5-(P(S)Ph 2 ) 2 Tz))(coe) 2 ] (coe = cyclooctene) was prepared upon reaction of potassium 4,5-bis(diphenylthiophosphinoyl)-1,2,3-triazolate with [Ir(coe) 2 (μ-Cl)] 2 . Its phosphorus derivatives were susceptible of oxidative addition processes.