NDLI: Diverse reactivity of a tricoordinate organoboron L<sub>2</sub>PhB: (L = oxazol-2-ylidene) towards alkali metal, group 9 metal, and coinage metal precursors

Content Provider	Royal Society of Chemistry (RSC)
Author	Kong, Lingbing Ganguly, Rakesh Kinjo, Rei Li, Yongxin
Copyright Year	2015
Abstract	The 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.
Starting Page	2893
Ending Page	2902
Page Count	10
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	6
Issue Number	5
Journal	Chemical Science
DOI	10.1039/c5sc00404g
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Persistent carbene Gold(I) chloride Hydrogen Ligand Boranylium ions Carbon\u2013hydrogen bond activation Alkali metal Reducing agent Coordination complex Gold chloride X-ray crystallography Boron Carbene Chloride Rhodium Natural Bond Orbital NBO Iridium Li Organoboron chemistry
Content Type	Text
Resource Type	Article
Subject	Chemistry

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