Reactivity of rhodium and iridium peroxido complexes towards hydrogen in the presence of B(C 6 F 5 ) 3 or [H(OEt 2 ) 2 ][B{3,5-(CF 3 ) 2 C 6 H 3 } 4 ]

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...

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Published inDalton transactions : an international journal of inorganic chemistry Vol. 47; no. 45; pp. 16299 - 16304
Main Authors Baumgarth, Hanna, Meier, Gregor, von Hahmann, Cortney N, Braun, Thomas
Format Journal Article
LanguageEnglish
Published England Royal Society of Chemistry 22.11.2018
Subjects
Hydrogen peroxide
Hydrogen storage
Iridium
Rhodium
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Summary: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).
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ISSN:1477-9226
1477-9234
DOI:10.1039/c8dt03853h