Thioether-functionalized aminosilanes R2Si(NH-C6H4-2-SR′)2 with R=Me, Ph and R′=t-Bu, Me, Ph were synthesized from the corresponding dichlorosilanes R2SiCl2 and lithiated aniline derivatives LiNH-C6H4-2-SR′. Treatment of the functionalized aminosilanes R2Si(NH-C6H4-2-SR′)2 with two eq. of n-BuLi and subsequent reaction with nickel(II) halides NiX2 (X=Cl, Br) or [Ni(acac)2(TMEDA)] led to the formation of the Ni(II) complexes [Ni{R2Si(N-C6H4-2-SR′)2}]. The X-ray single-crystal structure determinations of the nickel complexes revealed that the thioether-functionalized silylamides R2Si(NC6H4-2-SR′)22− act as tetradentate ligands. The nickel atoms exhibit a distorted square-planar coordination with Ni–N and Ni–S bond lengths in the range of 186.4(3)–186.9(2) pm and 217.5(1)–221.5(1) pm, respectively.
Treatment of molybdenum(II) acetate with thioether functionalized silylamides R2Si(NLi‐C6H4–2‐SR')2 leads to the formation of dinuclear MoII complexes [Mo2{R2Si(NC6H4‐2‐SR')2}2]. According to X‐ray crystal structure analyses the complexes [Mo2{Me2Si(NC6H4‐2‐SMe)2}2] and [Mo2{Ph2Si(NC6H4‐2‐SPh)2}2] comprise a Mo2‐unit which is coordinated by two μ‐κ‐N,N' silylamide ligands. The coordination sphere around the molybdenum atoms consists of two amide nitrogen atoms and two thioether sulfur atoms in a distorted square‐planar arrangement. The Mo‐Mo distances are 211.0(1) and 211.7(1) pm, resp. In the complex [Mo2{Ph2Si(NC6H4‐2‐SMe)2}2] the silyl amide units act as tetradentate κ‐N,N',S,S'chelating ligands and the Mo‐Mo distance is 218.6(1) pm.
Treatment of molybdenum(II) chloride with the difunctional silylamide Li2Me2Si(NPh)2 led to the formation of the tetranuclear cluster compound [Mo4{Me2Si(NPh)2}4]. According to the X‐ray crystal structure determination, the central core of the cluster consists of four molybdenum atoms in a nearly rectangular arrangement. There are two μ4‐κ‐N,N,N',N'‐Me2Si(NPh)22– ligands capping the Mo4 rectangle and two μ2‐Me2Si(NPh)22– ligands located at opposite edges. The alternating Mo–Mo distances of 218.1(1) and 279.5(1) pm indicate the presence of a cyclobutadiyne type cluster with alternating Mo–Mo triple and single bonds.
The trifunctional silylamine MesSi(NHPh)3 (Mes: 2,4,6-trimethylphenyl) was prepared by standard methods from MesSiCl3 and LiNHPh. Lithiation of MesSi(NHPh)3 and subsequent reaction with copper(I) benzoate afforded the nonanuclear cluster complex [Cu9{MesSi(NPh)3}2 (PhCO2)3]·2toluene. The cluster core consists of three copper atoms which are coordinated almost linearly by the nitrogen atoms of two adjacing MesSi(NPh)3 units. Additionally, each of the silylamide nitrogen atoms is connected to a peripheral copper atom and the peripheral copper atoms are linked by μ2-κ(O,O′) bridging benzoate groups. The observed Cu–N distances are in the range 189.6(4)–196.7(3) pm.
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