Gold(I) and Silver(I) Complexes with Thioether Functionalized Silylamido Ligands

Abstract

The thioether functionalized aminosilanes Me2Si(NH‐C6H4‐2‐SR)2 (R = Ph, Me) were lithiated with nBuLi and subsequently reacted with AgCl in the presence of PMe3 or with [AuCl(PMe3)]. In the case of Me2Si(NH‐C6H4‐2‐SPh)2 the dinuclear complexes [M2{Me2Si(NC6H4‐2‐SPh)2}(PMe3)2] (M = Ag; Au) were isolated. The analogous reactions starting from Me2Si(NH‐C6H4‐SMe)2 afforded the dinuclear gold complex [Au2{Me2Si(NC6H4‐2‐SMe)2}(PMe3)2] and the tetranuclear silver complex [Ag4{Me2Si(NC6H4‐2‐SMe)2}2(PMe3)2]. In the dinuclear compounds of the type [M2{Me2Si(NC6H4‐2‐SR)2}(PMe3)2], each of the silylamide N atoms is connected to a M(PMe3) group to give a nearly linear N–M–P arrangement with Ag–N and Au–N bonds in the range of 212.0(4)–213.3(4) pm and 205.3(3)–208.1(9) pm, respectively. [Ag4{Me2Si(NC6H4‐2‐SMe)2}2(PMe3)2] consists of a central Si2N4Ag2 ring with linearly coordinated Ag atoms (Ag‐N: 223.1(4)–222.1(4) pm) and two peripheral Ag(PMe3) units, which are connected to the amido N atoms in a chelating mode. The relatively short transannular Ag···Ag separation (277.6(1) pm) within the Si2N4Ag2 ring hints for argentophilic interactions. The peripheral Ag atoms are three coordinated with Ag–N distances of 233.9(4)–242.8(4) pm.

Ni(II) complexes with thioether-functionalized silylamide ligands. Synthesis and crystal structures of [Ni{Me2Si(N-C6H4-2-S-t-Bu)2}], [Ni{Ph2Si(N-C6H4-2-SMe)2}] and [Ni{Ph2Si(N-C6H4-2-SPh)2}]

“…The first studies go back to 2004 when Passarelli et al synthesized functionalized silylamides [Me 2 Si(NCH 2 CH 2 X) 2 ] 2− (X = OR, NR 2 ) and applied them for the generation of zirconium polymerization catalysts [5]. Recently, we found that thioether-functionalized silylamides [Me 2 Si(N-C 6 H 4 -2-SR′) 2 ] 2− (R′ = Me, Ph) can be successfully used for the synthesis of Cu(I), Ag(I), Au(I), and Tl(I) complexes [6,7]. Particularly in the case of the Cu(I), Ag(I) and Au(I) compounds, the presence of thioether side arms leads to an improved thermal stability.…”

“…7)-S-Ni 110.9 (1), C(6)-S-C(7) 102.2(1). (Dipp = 2,6-iPr 2 C 6 H 3 , 181.8(3) pm)[12], [Ni(NMesBMes 2 ) 2 ] (Mes = 2,4,6-Me 3 -C 6 H 2 , 186.5(2)-186 7[13], [Ni{N(SiMe 3 )(Dipp)} 2 ] (179.9(1) pm)[14].…”

Dinuclear Molybdenum(II) Complexes with Thioether Functionalized Silylamide Ligands

“…: Me 2 Si(NHC 6 H 4 ‐2‐SPh) 2 : 173.2(2) pm; Me 2 Si(NHC 6 H 4 ‐2‐S t Bu) 2 : 172.3(2) pm] and silylamide complexes [e.g. : Tl 2 Me 2 Si(NHC 6 H 4 ‐2‐SPh): 172(1)–173(1) pm, Ag 2 {Me 2 Si(NHC 6 H 4 ‐2‐SPh) 2 }(PMe 3 ) 2 : 171.2(4)–173.3(4) pm] . The most important difference between compound 3 and the other complexes 1 and 2 arises from the small N–Si–N angle (92.1°) due to the formation of the four‐membered SiN 2 Mo ring.…”

“…Molybdenum(II)‐acetate and the aminosilanes Me 2 Si(NHC 6 H 4 ‐2‐SMe) 2 and Ph 2 Si(NHC 6 H 4 ‐2‐SR) 2 (R = Me, Ph) were prepared according to literature methods.…”

“…The first and only report on molybdenum complexes with R 2 Si(NR') 2 2– ligands goes back to 2006 when Tsai et al described the synthesis and the crystal structures of [Mo 2 Cl 2 {Me 2 Si(NDipp) 2 } 2 ] and [Mo 2 {Me 2 Si(NDipp) 2 } 2 ] (Dipp = 2,6‐diisopropylphenyl) . Our studies on molybdenum silylamide complexes were initiated by the observation that functionalized silylamides with thioether donor groups of the type [R 2 Si(NC 6 H 4 ‐2‐SR') 2 ] 2– are useful ligands for the synthesis of di‐ and polynuclear copper(I), silver(I), gold(I) and thallium(I) complexes , . The presence of the intramolecularly coordinating thioether groups leads to a markedly improved thermal stability of the Cu I , Ag I , and Au I silylamides.…”