Structural Elucidation of Silver(I) Amides and Their Application as Catalysts in the Hydrosilylation and Hydroboration of Carbonyls

Abstract

This study details the isolation and characterisation of three novel silver(I) amides in solution and solidstate, [Ag(Cy 3 P)(HMDS)] 2,[ Ag(Cy 3 P){N(TMS)(Dipp)}] 3 and [Ag(Cy 3 P) 2 (NPh 2 )] 4.T heir catalytic abilities have proved successfuli nh ydroboration and hydrosilylation reactions with af ull investigation performed with complex 2.B oth protocols proceed under mild conditions, displaying exceptional functional-groupt olerance and chemoselectivity, in excellent conversions at competitive reactiont imes. This work reveals the first catalytic hydroboration of aldehydes and ketones performed by as ilver(I) catalyst.

Zinc Hydride-Catalyzed Hydrofuntionalization of Ketones

“…(1-(4-Nitrophenyl)ethoxy)diphenylsilane (4w). 34 NMR yield: (>99%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.22−8.20 (d, J = 7.9 Hz, 2H), 7.69−7.62 (m, 4H), 7.55−7.53 (d, J = 8.0 Hz, 2H), 7.48−7.42 (m, 6H), 5.51 (s, 1H), 5.16 (q, J = 6.5 Hz, 1H), 1.58−1.57 (d, J = 6.4 Hz, 3H).…”

A Green Synthesis of Carbene‐Metal‐Amides (CMAs) and Carboline‐Derived CMAs with Potentin vitroandex vivoAnticancer Activity

“…An "outside the box" application, is the use of amido complexes (including CMAs) as simple Brønsted-basic complexes which act as pre-catalysts in certain catalytic reactions. [25][26][27][28][29] An early example was disclosed by Bergmann and co-workers involving more traditional and far more reactive/unstable amido complexes. [26] We recently applied this concept for the first time using a carbazole-based CMA in the gold-catalyzed hydrofluorination of alkynes.…”

Simple Synthetic Routes to Carbene‐M‐Amido (M=Cu, Ag, Au) Complexes for Luminescence and Photocatalysis Applications

“…In the case of Cu, amido complexes bearing phosphines have been synthesized using lithium amides or by using KHMDS as the base, [25] while NHC‐bearing complexes have been synthesized by addition of amines to a [CuMe(NHC)] complex (Me=methyl) and later by using CsOH [26] . In the case of Ag, the amine lithiation approach was recently described for the synthesis of phosphine‐stabilized Ag‐amido complexes [27] . All of these synthetic routes have been described in the literature as straightforward and practical on a small scale, yet in reality these have important flaws with regard to sustainability, atom‐ and step‐economy and operational simplicity.…”

“…[26] In the case of Ag, the amine lithiation approach was recently described for the synthesis of phosphine‐stabilized Ag‐amido complexes. [27] All of these synthetic routes have been described in the literature as straightforward and practical on a small scale, yet in reality these have important flaws with regard to sustainability, atom‐ and step‐economy and operational simplicity. For example, the use of strong bases requires strictly inert conditions, excluding air and moisture, regardless of the stability of the initial or final organometallic materials.…”