Transformation of Thiolatogold(I) to an Au Complex with an (Arylthio)silyl Ligand. Use of an (Aminosilyl)boronic Ester as a Silylene Precursor

Abstract

P{ 1 H} NMR), and DFT calculations (PDF) Coordinates of results of the theoretical calculations (XYZ) Accession CodesCCDC 1999367−1999369 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk

Stepwise Polymetalation around an sp3 Benzyl Carbon Atom

“…Then, according to the intrinsic reaction coordinate (IRC) verification, we observed the cleavage of the C–Si bond in intermediate INT2 , which is simultaneously accompanied by the approach of the Si atom to a gold center with a short Au–Si distance of 2.431 Å. The calculated agostic Au–Si interaction in INT2 has a featured distance similar to those of reported unidentate Au–Si bonds . Finally, the approach of BF 4 – to INT2 readily generates the trinuclear intermediate INT4 by the removal of Me 3 SiF and BF 3 –MeOH.…”

Silyl(silylene) Coinage Metal Complexes Obtained from Isolable Cyclic Alkylsilylenes

“…In both complexes 3 and 4 , the Si1–M–Si2 angle decreases in the order Cu < Au < Ag [ 3 Cu (168.34(2)°) < 3 Au (165.75(6)°) < 3 Ag (164.23(11)°); 4 Cu (175.93(4)°) < 4 Au (172.886(19)°) < 4 Ag (171.544(16)°)]. In all complexes 3 and 4 , the Si1­(silylene)–M and Si2­(chlorosilyl)–M distances are comparable to or slightly longer than the previously reported silylene–M bond lengths [M = Cu (2.172–2.295 Å), ,,,,,,,, Ag (2.322–2.424 Å), ,,,, Au (2.242–2.318 Å) ,,, ] and neutral silyl–M­(I) bond lengths [M = Cu (2.211–2.363 Å), Ag (2.383–2.424 Å), , Au (2.344–2.362 Å) , ]. The Si1­(silylene)–M distances of CDASi-ligated complexes 3 Ag [2.4098(19) Å] and 3 Au [2.3297(16) Å] are shorter than those of CAASi-ligated complexes 4 Ag [2.4296(5) Å] and 4 Au [2.3512(6) Å], respectively, despite the larger steric demand of CDASi 1 than CAASi 2 [the percent buried volume (% V bur ): 38.2% for 1 and 35.4% for 2 ] .…”

Di- and Trinuclear Complexes of Pd(0) and Pt(0) with Bridging Silylene Ligands: Structures with a Coordinatively Unsaturated Metal Center and Their Reactions with Alkynes

“…However, the activation of the (aminosilyl)­boronic ester by Pd(0) and Pt(0) complexes has not been fully investigated to date. The reaction of the (aminosilyl)­boronic ester with an Au­(I)–thiolate complex yielded complexes with a diphenyl­(thiolate)­silyl ligand . The results of our theoretical calculations suggest that the reaction involves activation of the Si–B bond in the substrate and formation of the intermediate Au­(I) complex bearing an amine-stabilized silylene ligand.…”

“…The reaction of the (aminosilyl)boronic ester with an Au(I)−thiolate complex yielded complexes with a diphenyl(thiolate)silyl ligand. 15 The results of our theoretical calculations suggest that the reaction involves activation of the Si−B bond in the substrate and formation of the intermediate Au(I) complex bearing an amine-stabilized silylene ligand. In this paper, we report the reactions of (aminosilyl)boronic esters with Pd(0) and Pt(0) complexes with PCy 3 ligands and the formation of new types of di-and trinuclear complexes of these metals bearing bridging silylene ligands.…”