Issue 71, 2015

Hydrogen and oxygen activation by an iridium precursor containing the 4,5-bis(diphenylthiophosphinoyl)-1,2,3-triazolate ligand

Abstract

The novel mononuclear complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(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)Ph2)2Tz]. Reaction of [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(coe)2] with two equivalents of PPh3 led to complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(PPh3)2]; which, upon exposure to atmospheric air at room temperature, fixed molecular oxygen to produce complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(PPh3)2O2]. Molecular hydrogen also added oxidatively to complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(PPh3)2] to form the Ir(III) dihydride complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(PPh3)2(H)2]. Carbon–hydrogen bond activation was effected when complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(coe)2] was made to react with triphenylphosphite to give the ortho-metallated complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(P(OC6H4)(OPh)2)(P(P(OPh)3)(H)]. The new compounds were characterized by spectroscopic methods and, excepting for [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(PPh3)2], by single crystal X-ray analysis. Oxygen and hydrogen activation by the diphosphane complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(PPh3)2] compared with the inertness of the diolefin complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(coe)2] to such processes was assessed by means of a DFT-QTAIM analysis.

Graphical abstract: Hydrogen and oxygen activation by an iridium precursor containing the 4,5-bis(diphenylthiophosphinoyl)-1,2,3-triazolate ligand

Supplementary files

Article information

Article type
Paper
Submitted
27 Apr 2015
Accepted
26 Jun 2015
First published
29 Jun 2015

RSC Adv., 2015,5, 58046-58054

Hydrogen and oxygen activation by an iridium precursor containing the 4,5-bis(diphenylthiophosphinoyl)-1,2,3-triazolate ligand

M. Hernández-Juárez, R. A. Toscano, F. Cortés-Guzmán and N. Zúñiga-Villarreal, RSC Adv., 2015, 5, 58046 DOI: 10.1039/C5RA07698F

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