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Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions

TitleMixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions
Publication TypeJournal Article
Year of Publication2014
AuthorsXu, SC, Manna, K, Ellern, A, Sadow, AD
JournalOrganometallics
Volume33
Pagination6840-6860
Date Published12
Type of ArticleArticle
ISBN Number0276-7333
Accession NumberWOS:000346114900017
Keywords(hbpz(3))rh(co)(2) pz=3,5-dimethylpyrazolyl, 14-electron rh(iii), asymmetric, carbene complexes, catalysis, dynamic-behavior, h bond activation, insertion reactions, intermolecular c-h, iron, nitrido complex, ray crystal-structure
Abstract

CH2}RhH(CO) (12) and {PhB(Ox(Me2))(2)Im(Mes)}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis-[Ir](H)(Ph) complex. Alternatively, the rhodium carbonyl 5 or iridium isocyanide {PhB(Ox(Me2))(2)Im(Mes)}Ir(CO)CNtBu (15) reacts with PhSiH3 in the dark to form the silyl compound {PhB(Ox(Me2))(2)Im(Mes)}RhH(SiH2Ph)CO (14) or {PhB(Ox(Me2))(2)Im(Mes)}IrH(SiH2Ph)CNtBu (17). These examples demonstrate the enhanced thermal reactivity of {PhB(Ox(Me2))(2)Im(Mes)}-supported iridium and rhodium carbonyl compounds in comparison to tris(oxazolinyl)borate, tris(pyrazolyl)borate, and cyclopentadienyl-supported compounds.

DOI10.1021/om500891h
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3D Catalysis