A variety of isolable, 2 : 1 and 1 : 1 copper(i)–alkyne complexes of containing pyrazolate ligand supports are presented as well as the copper pyrazolate mediated acetylenic C–H and alkyne CC bond functionalizations.

Iron(0) pentacarbonyl complexes of gold(I), [Mes PAu-Fe(CO) ][SbF ] (1) and [(IPr*)Au-Fe(CO) ][SbF ] (2) (Mes=2,4,6-trimethylphenyl; IPr*=1,3-bis(2,6-bis(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene) have been synthesized using Mes PAuCl and (IPr*)AuCl as the gold(I) precursor, AgSbF halide ion abstractor, and the Lewis base Fe(CO) . The Au-Fe bond lengths of these metal-only Lewis pair complexes are significantly shorter than the sum of the experimentally derived covalent radii of Au and Fe. The v̄(CO) bands of the molecules show a notable blueshift relative to those observed for free Fe(CO) , indicating a substantial reduction in Fe→CO backbonding upon its coordination to gold(I) with either Mes P or IPr* supporting ligands (L). The analysis of the electronic structure with quantum chemical method suggests that the Au-Fe bond consists mainly of [LAu] ←Fe(CO) σ-donation and weaker [LAu] →Fe(CO) π-backdonation. The donor strength of Fe(CO) is similar to that of CO.

Organic azide complexes of copper­(I) and silver­(I), [(SIPr)­CuN­(1-Ad)­NN]­[SbF6], [(SIPr)­CuN­(2-Ad)­NN]­[SbF6], [(SIPr)­CuN­(Cy)­NN]­[SbF6], and [(SIPr)­AgN­(1-Ad)­NN]­[SbF6] have been synthesized by using Ag­[SbF6] and the corresponding organic azides with (SIPr)­CuBr and (SIPr)­AgCl (SIPr = 1,3-bis­(2,6-diisopropylphenyl)­imidazolin-2-ylidene). The copper and silver organic azide complexes were characterized by various spectroscopic techniques and X-ray crystallography. Group trends of isoleptic Cu­(I), Ag­(I), and Au­(I) organic azide complexes are presented on the basis of experimental data and a detailed computational study. The νasym(N3) values of the metal-bound 1-AdNNN in [(SIPr)­MN­(1-Ad)­NN]+ follow the order Ag < Cu < Au. DFT calculations show that gold­(I) forms the strongest bond with 1-AdNNN in this series, while silver has the weakest interaction. Furthermore, auxiliary ligand free coinage metal N-heterocyclic carbene complexes, [(SIPr)­M]­[SbF6], have been synthesized via metathesis reactions of (SIPr)­MCl (M = Cu, Ag, Au) with Ag­[SbF6]. X-ray crystal structures of dinuclear [(SIPr)­Ag]2[SbF6]2 and [(SIPr)­Au]2[SbF6]2 are also reported. They show close metallophilic contacts. [(SIPr)­Au]2[SbF6]2 reacts with OEt2, SMe2, and CN t Bu to afford [(SIPr)­Au­(OEt2)]­[SbF6], [(SIPr)­Au­(SMe2)]­[SbF6], and [(SIPr)­Au­(CN t Bu)]­[SbF6] adducts, respectively.

Fluorinated 1,3,5-triazapentadienyl complexes of copper catalyze the oxidation PAHs to quinones using H2O2 as an oxidant under mild conditions.

Metallo adducts involving Cu(i), Ag(i) and Au(i) Lewis acids and iron and manganese centered organometallic Lewis bases have been investigated using phosphine and N-heterocyclic carbene supporting ligands.

Fluorinated bis-and tris(pyrazolyl)boratocopper complexes catalyze the nitrene insertion to CÀ H bonds of aromatic hydrocarbons efficiently producing amination products in good to excellent yields at room temperature. Imidoiodanes, PhI=NTs (Ts = p-toluenesulfonyl) and PhI=NNs (Ns = p-nitrophenylsulfonyl) serve as the nitrene source. The bis(pyrazolyl)borate catalyst [H 2 B(3,5-(CF 3 ) 2 Pz) 2 ]Cu(NCMe) with PhI=NNs produced the arene CÀ H functionalized product of mesitylene in 87 % yield with only trace amounts of benzylic CÀ H insertion. The use of [H 2 B (3,5-(CF 3 ) 2 -4-(NO 2 )Pz) 2 ]Cu(NCMe) that has an even weakly donating pyrazolate generated the arene CÀ H insertion product exclusively. The tris(pyrazolyl)borate complex [HB(3,5-(CF 3 ) 2 Pz) 3 ] Cu(NCMe), in contrast, generated the benzylic amination product from mesitylene and PhI=NNs in 82 % yield with only very minor amounts of arene CÀ H functionalization. DFT calculations suggest that Cu-nitrene moiety generated from [HB (3,5-(CF 3 ) 2 Pz) 3 ]Cu(NCMe) and PhI=NNs activates the benzylic CÀ H bond of mesitylene via a hydrogen atom abstraction (HAA) followed by a radical rebound (RR) pathway, whereas the functionalization of sp 2 CÀ H bonds of mesitylene by [H 2 B(3,5-(CF 3 ) 2 Pz) 2 ]Cu(NNs) ensues possibly via a nitrene addition to the arene core.[a] T.

Zinc complexes [{(3,5-(CF)Pz)ZnEt}(μ-THF)] (1), [{(3-(CF),5-(t-Bu)Pz)ZnEt}(μ-THF)] (2), and [{(3,5-(i-Pr)Pz)ZnEt}(μ-THF)] (3) adopt dinuclear structures with zinc sites bridged by a THF molecule and two pyrazolate ligands. The zinc complex 1 that features the weakest donating pyrazolate is the best catalyst among the three for the aziridination of styrene and cis-cyclooctene with PhI[double bond, length as m-dash]NTs.

We report the synthesis, characterization and computational analysis of coinage metal-ether and related –OH2 complexes supported by N-heterocyclic carbenes (NHC), SIPr and Et2CAAC.