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Formation and Site-Selective Reactivity of a Nonsymmetric Dinuclear Iridium BisMETAMORPhos Complex

By Sander Oldenhof (1569832), Frederic G. Terrade (1569835), Martin Lutz (1234866), Jarl Ivar van der Vlugt (1569838) and Joost N. H. Reek (1319472)

Abstract

A flexible di­(sulfonamidophosphine) ligand (<b>1</b><sup><b>H2</b></sup>, Ph<sub>2</sub>PN<sup>H</sup>S­(O)<sub>2</sub>N<sup>H</sup>PPh<sub>2</sub>) was synthesized from commercially available sulfamide and chlorodiphenylphosphine. Coordination of this new bisMETAMORPhos <b>1</b><sup><b>H2</b></sup> with [Ir­(Cp*)­Cl­(μ-Cl)]<sub>2</sub> instantly led to the formation of the P,P-coordinated bimetallic complex <b>2</b> [Ir­(Cp*)­Cl­(κ<sup>1</sup>-<i>P</i><sub>1</sub>; κ<sup>1</sup>-<i>P</i><sub>2</sub>-<b>1</b><sup><b>H2</b></sup>)­Ir­(Cp*)­Cl]. Reaction of <b>2</b> using excess NaOAc led to the formation of nonsymmetric homodinuclear complex <b>3</b> [Ir­(Cp*)­Cl­(κ<sup>2</sup>-<i>P</i>,<i>O</i>; κ<sup>3</sup>-<i>P</i>,<i>N</i>,<i>C</i>; μ-<b>1</b>)­Ir­(Cp*)], which contains two distinctly different Ir<sup>III</sup> centers, with a <i>fac</i>-<i>P</i>,<i>N</i>,<i>C</i> and a <i>fac</i>-<i>P</i>,<i>O</i>,<i>Cl</i> coordination environment. The ligand is overall trisanionic due to additional intramolecular C–H activation of a flanking phenyl ring. Complex <b>3</b> reacts selectively at the Ir­(<i>P</i>,<i>O</i>,<i>Cl</i>) center with a single equivalent of HCl or H<sub>2</sub> to generate complexes <b>4</b> and <b>5</b>, respectively. These complexes are generated via heterolytic cleavage of the H–Cl or H–H bond, which reprotonates the ligand showing its bifunctional applicability. The Ir–C bond is found to be inert under these conditions

Topics: Biophysics, Biochemistry, Microbiology, Cell Biology, Molecular Biology, Physiology, Marine Biology, Cancer, Biological Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, 2PNHS, ligand, nonsymmetric homodinuclear, bisMETAMORPhos 1 H 2, Nonsymmetric Dinuclear Iridium BisMETAMORPhos ComplexA, heterolytic cleavage, complexes 4, formation, H 2, phenyl ring, Complex 3, bifunctional applicability, IrIII centers
Year: 2015
DOI identifier: 10.1021/acs.organomet.5b00249.s003
OAI identifier: oai:figshare.com:article/2150857
Provided by: FigShare
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