Title | Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions |
Publication Type | Journal Article |
Year of Publication | 2014 |
Authors | Xu, SC, Manna, K, Ellern, A, Sadow, AD |
Journal | Organometallics |
Volume | 33 |
Pagination | 6840-6860 |
Date Published | 12 |
Type of Article | Article |
ISBN Number | 0276-7333 |
Accession Number | WOS: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. |
DOI | 10.1021/om500891h |
Custom 1 | 3D Catalysis |