Synthesis, structural characterization and thermal properties of copper and silver silyl complexes

Abstract

The synthesis of copper and silver silyl complexes containing either N-heterocyclic carbenes or nitrogen donors is described. Alterations made to both the neutral donor ligands as well as the silyl group provided access to a number of different compounds. Many of the complexes synthesized were studied in the solid state and the effect of the donor ligand on the final structure of the complexes was examined. The thermal properties of the complexes were explored using thermogravimetric analysis, differential scanning calorimetry and sublimations. Some of the complexes synthesized were demonstrated to be promising volatile metal precursors.

NHC Adducts of Disilylated Germylenes and Stannylenes and Their Coordination Chemistry with Group 11 Metals

“…The longer Sn–Au bond reflects the neutral stannylene adduct character of the ligand in contrast to the anionic cyanostannyl ligand of 10 . Reported values for Si‐Au distances are between 2.352 and 2.401 Å, and for 13 and 12 (Figure and Figure ) these are a little bit shorter (Table ). Complexes 12 , 13 , and 15 (Figure ) are the first examples containing the structural motives Ge–Au–Si, Sn–Au–Si, and Ge–Ag–Si.…”

NHC Supersilyl Silver Complex [Ag(IPr)SitBu3] as a Promising Agent for Substitution Reactions

“…Besides two other silyl complexes [Ag(IPr)SiEt(SiMe 3 ) 2 ] and [Ag(IPr)Si(SiMe 3 ) 3 ], the supersilyl silver complex 1 is the third IPr silyl silver complex which could be characterized by X‐ray crystallography. Due to the bulky supersilyl group the Si–Ag distance in 1 [Si–Ag 2.4244(9) Å] is somewhat longer than the appropriate Si–Ag bonds found in [Ag(IPr)SiEt(SiMe 3 ) 2 ] [Si–Ag bond lengths: 2.4006(6) Å] and [Ag(IPr)Si(SiMe 3 ) 3 ] [Si–Ag bond lengths: 2.3936(5) Å], respectively. One of the t Bu groups in 1 is disordered over two position with a site occupation factor of 0.521(9) for the major occupied site.…”

“…The complex 1 is located on a crystallographic mirror plane with only half a molecule in the asymmetric unit. Besides two other silyl complexes [Ag(IPr)SiEt(SiMe 3 ) 2 ] [13] and [Ag(IPr)Si(SiMe 3 ) 3 ], [13] the supersilyl silver complex 1 is the third IPr silyl silver complex which could be characterized by X-ray crystallography. Due to the bulky supersilyl group the Si-Ag distance in 1 [Si-Ag 2.4244(9) Å] is somewhat longer than the appropriate Si-Ag bonds found in [Ag(IPr)SiEt(SiMe 3 ) 2 ] [Si-Ag bond lengths: 2.4006(6) Å] [13] and…”

“…[Ag(IPr)Si(SiMe 3 ) 3 ] [Si-Ag bond lengths: 2.3936(5) Å], [13] respectively. One of the tBu groups in 1 is disordered over two position with a site occupation factor of 0.521(9) for the major occupied site.…”

“…The molecules of 1 are arranged in an alternate fashion, as shown in Figure 3. (13), C(4)#1-Si(1)-C(4) 111.0(3), C(3)-Si(1)-Ag(1) 110.79 (13), C(4)-Si(1)-Ag(1) 109.21 (12), C(1)-N(1)-C(2) 111.94 (19), C(1)-N(1)-C(11) 122.34 (17), C(2)-N(1)-C(11) 125.63 (19), N(1)-C(1)-N(1)#1 103.7(2), N(1)-C(1)-Ag(1) 128.15 (12). Symmetry transformation used to generate equivalent atoms: #1 x, -y + 1/2, z.…”