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Gold(I) and Silver(I) Complexes with Thioether Functionalized Silylamido Ligands
Author(s) -
Liebing Phil,
Merzweiler Kurt
Publication year - 2017
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201700283
Subject(s) - thioether , ring (chemistry) , chemistry , chelation , crystallography , stereochemistry , inorganic chemistry , organic chemistry
The thioether functionalized aminosilanes Me 2 Si(NH‐C 6 H 4 ‐2‐S R ) 2 ( R = Ph, Me) were lithiated with n BuLi and subsequently reacted with AgCl in the presence of PMe 3 or with [AuCl(PMe 3 )]. In the case of Me 2 Si(NH‐C 6 H 4 ‐2‐SPh) 2 the dinuclear complexes [ M 2 {Me 2 Si(NC 6 H 4 ‐2‐SPh) 2 }(PMe 3 ) 2 ] ( M = Ag; Au) were isolated. The analogous reactions starting from Me 2 Si(NH‐C 6 H 4 ‐SMe) 2 afforded the dinuclear gold complex [Au 2 {Me 2 Si(NC 6 H 4 ‐2‐SMe) 2 }(PMe 3 ) 2 ] and the tetranuclear silver complex [Ag 4 {Me 2 Si(NC 6 H 4 ‐2‐SMe) 2 } 2 (PMe 3 ) 2 ]. In the dinuclear compounds of the type [ M 2 {Me 2 Si(NC 6 H 4 ‐2‐S R ) 2 }(PMe 3 ) 2 ], each of the silylamide N atoms is connected to a M (PMe 3 ) 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. [Ag 4 {Me 2 Si(NC 6 H 4 ‐2‐SMe) 2 } 2 (PMe 3 ) 2 ] consists of a central Si 2 N 4 Ag 2 ring with linearly coordinated Ag atoms (Ag‐N: 223.1(4)–222.1(4) pm) and two peripheral Ag(PMe 3 ) 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 Si 2 N 4 Ag 2 ring hints for argentophilic interactions. The peripheral Ag atoms are three coordinated with Ag–N distances of 233.9(4)–242.8(4) pm.