N-heterocyclic carbene ligand SIDipp (SIDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) and trimesitylphosphine ligand have been used in the synthesis of gold(I) cyanide, t-butylisocyanide, and cyclooctyne complexes (SIDipp)Au(CN) (3), (Mes(3)P)Au(CN) (4), [(Mes(3)P)(2)Au][Au(CN)(2)] (5), [(SIDipp)Au(CN(t)Bu)][SbF(6)] ([6][SbF(6)]), [(SIDipp)Au(cyclooctyne)][SbF(6)] ([8][SbF(6)]), and [(Mes(3)P)Au(cyclooctyne)][SbF(6)] ([9][SbF(6)]). A detailed computational study has been carried out on these and the related gold(I) carbonyl adducts [(SIDipp)Au(CO)][SbF(6)] ([1][SbF(6)]), [(Mes(3)P)Au(CO)][SbF(6)] ([2][SbF(6)]), and [(Mes(3)P)Au(CN(t)Bu)](+) ([7](+)). X-ray crystal structures of 3, 5, [6][SbF(6)], [8][SbF(6)], and [9][SbF(6)] revealed that they feature linear gold sites. Experimental and computational data show that the changes in π-acid ligand on (SIDipp)Au(+) from CO, CN(-), CN(t)Bu, cyclooctyne as in [1](+), 3, [6](+), and [8](+) did not lead to large changes in the Au-C(carbene) bond distances. A similar phenomenon was also observed in Au-P distance in complexes [2](+), 4, [7](+), and [9](+) bearing trimesitylphosphine. Computational data show that the Au-L bonds of "naked" [Au-L](+) or SIDipp and Mes(3)P supported [Au-L](+) (L = CO, CN(-), CN(t)Bu to cyclooctyne) have higher electrostatic character than covalent character. The Au←L σ-donation and Au→L π-back-donation contribute to the orbital term with the former being the dominant component, but the latter is not negligible. In the Au-CO adducts [1](+)and [2](+), the cationic gold center causes the polarization of the C-O σ and π orbitals toward the carbon end making the coefficients at the two atoms more equal which is mainly responsible for the large blue shift in the CO stretching frequency. The SIDipp and Mes(3)P supported gold(I) complexes of cyanide and isocyanide also exhibit a significant blue shift in υ(CN) compared to that of the free ligands. Calculated results for Au(CO)Cl and Au(CF(3))CO suggest that the experimentally observed blue shift in ν(CO) of these compounds may at least partly be caused by intermolecular forces.
A new series of robust, user‐friendly, and highly active PEPPSI‐themed (pyridine‐enhanced precatalyst preparation, stabilization and initiation) (NHC)PdX2(pyridine)‐type (X = Cl, Br) precatalysts of C4–C5 saturated imidazole‐ (1–4) and triazole‐based (5 and 6) N‐heterocyclic carbenes for the Hiyama and Sonogashira couplings under amenable conditions are reported. Specifically 1–6 efficiently catalyze the fluoride‐free Hiyama coupling of aryl halides with PhSi(OMe)3 and CH2=CHSi(OMe)3 in air in the presence of NaOH as a base in a mixed aqueous medium (dioxane/H2O, 2:1 v/v). Along the same lines, these 1–6 precatalysts also promote the Cu‐free and amine‐free Sonogashira coupling of aryl bromides and iodides with phenylacetylene in air and in a mixed aqueous medium (DMF/H2O, 3/1 v/v). The complexes 1–6 were synthesized by the direct reaction of the respective imidazolinium and triazolium halide salts with PdCl2 in pyridine in the presence of K2CO3 as a base. DFT studies on the catalytically relevant palladium(0) (NHC)Pd(pyridine) precursors 1a–6a reveal significant donation from the N‐heterocyclic carbene lone pair onto the unfilled σ* orbital of the trans Pd–pyridine bond. This weakens the Pd‐bound “throwaway” pyridine ligand, and its dissociation marks the initiation of the catalytic cycle.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
A comparison is drawn between the nickel and palladium precatalysts of 1,2,4-triazole based N-heterocyclic carbenes in the hydroamination of activated olefins. Though all of the newly designed nickel and palladium precatalysts, trans-[1-i-propyl-4-R-1,2,4-triazol-5-ylidene](2)MBr(2) [R = Et, M = Ni (1b); R = Et, M = Pd (1c); R = CH(2)CH=CH(2), M = Ni (2b) and R = CH(2)CH=CH(2), M = Pd (2c)], are moderately active for hydroamination reaction of a variety of secondary amines viz. morpholine, piperidine, pyrrolidine and diethylamine with activated olefins like, acrylonitrile, methyl acrylate, ethyl acrylate and t-butyl acrylate at room temperature in 1 hour, the nickel complexes (1b and 2b) exhibited superior activity compared to its palladium counterparts (1c and 2c). The better performance of the nickel complexes has been correlated to the more electron deficient metal center in the nickel 1b and 2b complexes than in the palladium 1c and 2c analogs based on the density functional theory studies. The 1b-c and 2b-c complexes were synthesized by the reaction of 1-i-propyl-4-R-1,2,4-triazolium bromide [R = Et (1a) and R = CH(2)CH=CH(2) (2a)] with MCl(2) [M = Ni, Pd] in presence of NEt(3) as a base.
A series of highly efficient gold(I) precatalysts of 1,2,4-triazole based N-heterocyclic carbenes, [1-R-4-R'-1,2,4-triazol-5-ylidene]AuCl [R = CH(2)CO(t)Bu, R' = CH(2)Ph (1c); R = CH(2)CONH(t)Bu, R' = CH(2)Ph (2c); R = CH(2)CO(t)Bu, R' = CH(2)CO(t)Bu (3c), and R = C(6)H(10)OH, R' = CH(2)Ph (4c)] are reported for the hydroamination of terminal alkynes with a variety of sterically demanding o/p-substituted aryl amines yielding the corresponding ketimines in air. The gold 1c-4c complexes exhibited extremely high activity in comparison to the silver analogues 1b-4b, thereby highlighting the role of gold as a metal in the catalysis of the hydroamination reaction. Additionally, the 1,2,4-triazole based 1c-4c precatalysts showed significantly superior activity in comparison to the two representative imidazole analogues, namely, [1-(benzyl)-3-(N-t-butylacetamido)imidazol-2-ylidene]AuCl and [1-(2-hydroxy-cyclohexyl)-3-(benzyl)imidazol-2-ylidene]AuCl, thereby underscoring the importance of the 1,2,4-triazole based N-heterocyclic carbenes over the imidazole based ones in designing the gold(I) precatalysts for the hydroamination reaction. The gold(I) complexes (1c-4c) were synthesized by transmetalation reaction of the silver analogues 1b-4b with (SMe(2))AuCl in 60-76% yield while the silver 1b-4b complexes in turn were synthesized from the respective 1,2,4-triazolium halide salts by treatment with Ag(2)O in 43-64% yield.
Cationic gold carbonyl complexes supported by N-heterocyclic carbene ligands, SIDipp and IDipp, have been synthesized. [(SIDipp)Au(CO)][SbF(6)] has a linear, two-coordinate gold center. [(SIDipp)Au(CO)][SbF(6)] and [(IDipp)Au(CO)][SbF(6)] display ̃ν(CO) values at 2197 and 2193 cm(-1), respectively. Computational studies on [(SIMe)Au(CO)](+) indicate the presence of a strong Au(I)-CO bond.
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