dc.contributor.authorKong, Lingbing
dc.contributor.authorGanguly, Rakesh
dc.contributor.authorLi, Yongxin
dc.contributor.authorKinjo, Rei
dc.date.accessioned2015-08-19T08:20:24Z
dc.date.available2015-08-19T08:20:24Z
dc.date.copyright2015en_US
dc.date.issued2015
dc.identifier.citationKong, L., Ganguly, R., Li, Y.,& Kinjo, R. (2015). Diverse reactivity of a tricoordinate organoboron L2PhB: (L = oxazol-2-ylidene) towards alkali metal, group 9 metal, and coinage metal precursors. Chem. Sci., 6(5), 2893-2902.en_US
dc.identifier.issn2041-6520en_US
dc.identifier.urihttp://hdl.handle.net/10220/38469
dc.description.abstractThe reactivity of a tricoordinate organoboron L2PhB: (L = oxazol-2-ylidene) 1 towards metal precursors and its coordination chemistry were comprehensively studied. While the boron center in 1 is reluctant to coordinate to the alkali metals in their trifluoromethanesulfonate salts (MOTf) (M = Li, Na, K), the unprecedented compound 2 containing two L2PhB: units linked by a cyclic Li(OTf)2Li spacer was obtained from the reaction of 1 with LiOTf. Treatment of 1 with group 9 metal complexes [MCl(COD)]2 (M = Rh, Ir) afforded the first zwitterionic rhodium(I)–boronium complex 3 and the iridium(III)–borane complex 4, respectively. The reaction pathway may involve C–H activation followed by proton migration from the metals to the boron center, demonstrating the first example of the deprotonation of metal hydrides by a basic boron. In the reactions with coinage metals, 1 could act as a two-electron reducing agent towards the metal chlorides MCl (M = Cu, Ag, Au). Meanwhile, the reaction of 1 with gold chloride supported by a N-heterocyclic carbene (NHC) produced a heteroleptic cationic gold complex [(L2PhB)Au(NHC)]Cl (6) featuring both carbene and L2PhB: ligands on the gold atom. In contrast, an isolable gold chloride complex (L2PhB)AuCl (8) was obtained by direct complexation between 1 and triphenylphosphine-gold chloride via ligand exchange. X-ray diffraction analysis and computational studies revealed the nature of the B:→Au bonding interaction in complexes 6 and 8. Natural Population Analysis (NPA) and Natural Bond Orbital (NBO) analysis support the strong σ-donating property of the L2PhB: ligand. Moreover, preliminary studies showed that complex 8 can serve as an efficient precatalyst for the addition of X–H (X = N, O, C) to alkynes under ambient conditions, demonstrating the first application of a metal complex featuring a neutral boron-based ligand in catalysis.en_US
dc.language.isoenen_US
dc.relation.ispartofseriesChemical scienceen_US
dc.rights© 2015 The Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.en_US
dc.subjectDRNTU::Science::Chemistry::Crystallography::Chemical crystallography
dc.titleDiverse reactivity of a tricoordinate organoboron L2PhB: (L = oxazol-2-ylidene) towards alkali metal, group 9 metal, and coinage metal precursorsen_US
dc.typeJournal Article
dc.contributor.schoolSchool of Physical and Mathematical Sciencesen_US
dc.identifier.doihttp://dx.doi.org/10.1039/C5SC00404G
dc.description.versionPublished versionen_US
dc.contributor.organizationNTU-CBC Crystallography Facilityen_US


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