Silicon(II) Bis(trimethylsilyl)amide (LSiN(SiMe₃)₂, L = PhC(NtBu)₂) Supported Copper, Silver, and Gold Complexes

Abstract

The reactions of silicon­(II) bis­(trimethylsilyl)­amide (1; LSiN­(SiMe3)2, L = PhC­(NtBu)2) with the readily available CuI, AgOTf (Tf = SO2CF3), AgNO3, and AuCl­(SMe2) have been reported, which resulted in a series of silylene–coinage-metal complexes (2–5) with Si­(II)→coinage-metal bonds. Each compound has been characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction studies. X-ray analyses of 2 and 3 showed that they are dimeric in nature, featuring four-membered Cu2I2 and Ag2O2 rings, respectively. However, 4 and 5 are mononuclear complexes with a silylene ligand and possess only one SiII→Ag or SiII→Au bond, respectively. Prior to our contribution, there have been very few structurally authenticated silylene–silver and silylene–gold complexes known. Therefore, 2–5 are noteworthy additions to the Si­(II)–coinage-metal complexes.

Synthesis and Coordination Behavior of a New Hybrid Bidentate Ligand with Phosphine and Silylene Donors

“…Comparison with already reported Cu−X bond lengths (X=P, Si, Cl; see the Supporting Information) also suggests that compound 4 is diamagnetic and that copper chloride is not oxidized, but rather dissociates to Cu + and [CuCl 2 ] − . The Si1−Cu1 and Si2−Cu1 distances are 2.264 and 2.273 Å, which is comparable to other Si−Cu distances in copper(I) complexes [24] (see the Supporting Information). The P1−Cu1 and P2−Cu1 bonds are quite long, about 2.28–2.3 Å, which is actually comparable to Cu 0 −P bond lengths.…”

Synthetic Diversity and Luminescence Properties of ArN(PPh2)2‐Based Copper(I) Complexes

“…Since copper is a more appealing element as a luminescent dopant, because of its low cost and non‐toxicity, we decided to prepare analogous copper(I) complexes 1 and 2 with PNP ligands and compare their structural and photophysical properties. The reaction of Ph 2 PN(2,6‐Me 2 C 6 H 3 )PPh 2 ( L1 ) with copper bromide/chloride led to dimeric copper(I) complexes analogous to our recent report on silylene supported dimeric copper(I) complexes , . It has to be noted here that the reactions of simple (PPh 2 ) 2 NPh ligands with copper(I) halides led to tetrameric structures.…”

Carbazole Substituted Amidinato Silylene: Synthesis, Bonding, and Coordination Behavior with Coinage Metals

“…To start with, the equivalent reaction of 1 with AuCl·SMe 2 produced the complex 3 (Scheme ). The 29 Si NMR spectrum of 3 shows a peak at δ 9.0 ppm which is comparatively downfield shifted than the previously reported [PhC­(N t Bu) 2 Si­{N­(TMS) 2 }­AuCl] (δ 8.76 ppm) and upfield shifted than [PhC (N t Bu) 2 Si­{N­(PPh 2 )­(2,6- i Pr 2 C 6 H 3 )}­AuCl] (δ 24.73 ppm) Figure ).…”

“…However, a close look at the literature reveals very few monodentate N-donor substituted silylenes. Although benzamidinato silylene ligated coinage metal complexes have been isolated over the years, they are still in their early stages. − This encouraged us to synthesize a new N-donor substituted three coordinate benzamidinato silylene and compare the HOMO-LUMO gap and coordination properties with the reported analogues. For this purpose, we choose tricyclic carbazole (Cbz) as an N-donor precursor as it is the main structural moiety of many biologically active compounds, and it has found versatile applications in synthesizing dyes and pigments .…”