Development of Ligands and Metal Complexes With Weakly Coordinating Apical Elements and their Application to Nitrene Insertion and Addition to C‒h and C=c Bonds

"We present a family of triangular coinage metal M3Cl3 complexes [M = Cu (I), Ag (I)] supported by antimony [Sb (III)], and bismuth [Bi (III)]-centered highly basic tetramethyl-guanidinyl [TMG3trphen-E] (E = Sb, Bi) ligand frameworks with their applications as catalysts toward the construction of C‒N bond through aziridination and amination reaction methodologies.The [(TMG3trphen-Sb)Cu3(µ-Cl)3] catalyst gives better yields of aziridines with styrenes than [(TMG3trphen-Bi)Cu3(µ-Cl)3] with PhINTs as a nitrene source. However, the catalytic reactivity of both catalysts is enhanced by an electrophilic nitrene, PhINTces for the amination of C‒H bonds with sec-benzylic substrates. Their non-halogenated copper compounds [(TMG3trphen-E)2Cu2]2+2Y‒ (Y = PF6, B(C6F5)4) have been synthesized by the reaction of TMG3trphen-E ligand with halide-free Cu(I) sources or by dichlorination.Further, the tripodal ligand TMG3trphen-Bz has been synthesized in an electrophilic ligand development for incorporating weakly electron donor apical elements. The ligand possesses a 1,3,5-substituted benzene platform with TMG3trphen arms adopting a pseudo- C3-symmetric geometry. The catalyst [(TMG3trphen-Bz)Cu3(µ-Cl)3] has been subsequently synthesized by extracting a Cu3(µ-Cl)3 cluster from anhydrous CuCl and shown the reactivity for the amination of sec-benzylic C–H bonds of a panel of substrates.The reactivity of all [(TMG3trphen-E)Cu3(µ-Cl)3] catalysts for amination reactions have also been supported by Hammett analysis which reveals the development of a small positive charge during C–H bond activation"-- Abstract, p. iv