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Title

Reactivity of Me-pma RhI and IrI complexes upon deprotonation and their application in catalytic carbene carbonylation reactions

AuthorsTang, Zhou; Tejel, Cristina ; Martinez de Sarasa Buchaca, Marc; Lutz, Martin; Vlugt, Jarl Ivar van der; Bruin, Bas de
KeywordsRhodium
Iridium
Ketene
Ligand design
Redox chemistry
Carbenes
Issue Date2016
CitationEuropean Journal of Inorganic Chemistry 2016(7): 963-974 (2016)
AbstractDehydrogenative oxidation of amines is a relevant process in metal-mediated catalysis, with the amines being either substrates or ligands. Transformation of amine- into imine-type ligands in the coordination sphere of a transition metal can be an important catalyst activation process. The behaviour of secondary pyridin-2-ylmethanamine (pma) ligands in the corresponding rhodium and iridium complexes upon NH deprotonation varies, depending on a number of factors. In this paper the behaviour of the Me-pma ligand [Me-pma = N-methyl-1-(pyridin-2-yl)methanamine] bound to [Rh(cod)] and [Ir(cod)] was studied. Whereas the iridium amido complex could be obtained upon NH deprotonation, the rhodium complex instantaneously disproportionated into a free pma ligand and an unusual dinuclear complex, adopting a structure with two Rh metal centres hosted by a dianionic (pma-2H) ligand, and with the ligand coordinating to Rh2 as an >aza-allyl> fragment. The study gives further proof for the effect of pyridine ligation on the previously observed charge-transfer from the ligand to the metal. Furthermore, the catalytic activity of both the Ir and the Rh species with Me-pma in carbene carbonylation reactions to generate ketenes was studied.
URIhttp://hdl.handle.net/10261/155665
DOI10.1002/ejic.201501302
Identifiersdoi: 10.1002/ejic.201501302
e-issn: 1099-0682
issn: 1434-1948
Appears in Collections:(ISQCH) Artículos
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