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Reactivity of rhodium and iridium peroxido complexes towards hydrogen in the presence of B(C6F5)3 or [H(OEt2)2][B{3,5-(CF3)2C6H3}4]

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Abstract

The peroxido complexes trans-[M(4-C5F4N)(O2)(CNtBu)(PR3)2] (1: M = Rh, R = Et; 2a: M = Ir, R = iPr) can be used in the metal-mediated hydrogenation of O2. The reaction of trans-[Rh(4-C5F4N)(O2)(CNtBu)(PEt3)2] (1) with B(C6F5)3 and H2 gave trans-[Rh(4-C5F4N)(CNtBu)(PEt3)2] (3), OPEt3 and (H2O)·B(C6F5)3, whereas treatment of [H(OEt2)2][B{3,5-(CF3)2C6H3}4] with 1 in the presence of H2 yielded trans-[Rh(4-C5F4N)(CNtBu)(PEt3)2] (3) and H2O2. The reactivity of 2a towards B(C6F5)3 and BClCy2 was also studied and an intermediate was detected which is assigned to be trans-[Ir(4-C5F4N)(Cl)(OOBCy2)(CNtBu)(PiPr3)2] (4a).

Graphical abstract: Reactivity of rhodium and iridium peroxido complexes towards hydrogen in the presence of B(C6F5)3 or [H(OEt2)2][B{3,5-(CF3)2C6H3}4]

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Publication details

The article was received on 24 Sep 2018, accepted on 26 Oct 2018 and first published on 07 Nov 2018


Article type: Paper
DOI: 10.1039/C8DT03853H
Citation: Dalton Trans., 2018, Advance Article
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    Reactivity of rhodium and iridium peroxido complexes towards hydrogen in the presence of B(C6F5)3 or [H(OEt2)2][B{3,5-(CF3)2C6H3}4]

    H. Baumgarth, G. Meier, C. N. von Hahmann and T. Braun, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C8DT03853H

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