New amido and imido bridged complexes of copper - Syntheses and structures of [{Li(OEt2)}(2)][Cu(NPh2)(3)], [ClCuN(SnMe3)(3)], [{CuN(SnMe3)(2)}(4)], (1)(infinity)[Cu-16((NH2Bu)-Bu-t)(12)Cl-16], [{CuNh(t)Bu}(8)], [Li(dme)(3)][Cu-6(NHMes)(3)(NMes)(2)],

摘要

The reactions of stannylated and lithiated amines with coppersalts (halogenides, thiocyanates) lead to amido and imido bridged complexes which contain one to twelve metal atoms. [{Li(OEt2)}(2)][Cu(NPh2)(3)] (1) results from the reaction of CuCl with LiNPh2 in the presence of trimethylphosphine. With N(SnMe3)(3), CuCl reacts to the donor-acceptor complex [ClCuN(SnMe3)(3)] (2) that is transformed into the tetrameric complex [{CuN(SnMe3)(2)}(4)] (3) by thermolysis. 3 can also be obtained by the reaction of LiN(SnMe3)(2) with Cu(SCN)(2). While terminally bound in 1, the amido ligand is mu(2)-bridging between copper atoms in compound 3. The influence of the alkyl amide's leaving group can be seen from a comparison of the reactivity of (Me3SnNHBu)-Bu-t and (LiNHBu)-Bu-t, respectively. With (Me3SnNHBu)-Bu-t, CuCl2 forms the polymeric compound (1)(infinity)[Cu-16((NH2BU)-B-t)(12)Cl-16] (4) whereas in the case of (LiNHBu)-Bu-t with both CuCl and CuSCN, the complex [{(CuNHBu)-Bu-t}(8)] (5) is obtained. The latter contains two planar Cu4N4-rings similar to those in 3. If a mesityl group is introduced at the lithium amide, different products are accessible. Both, CuBr and CuSCN, lead to the formation of [Li(dme)(3)][Cu-6(NHMes)(3)(NMes)(2)] (6) whose anion consists of a prismatic copper core with mu(2)-bridging amido and mu(3)-bridging imido ligands. In the presence of PPh4Cl, a mixture of Cu(SCN)(2) and LiNHMes enables an ortho-metallation reaction that produces [PPh3(C6H4)-CuNHMes] (7). From the reaction of CuSCN with LiNHMes and LiNHPh either the dimeric complex [{Li(dme)]-[Cu(NHMes)(NHPh)}(2)] (8) or the cluster [{Li(dme)(3)}(3)]-[Li(dme)(2)][Cu-12(NPh)(8)] (9) results. The anion in 9 exhibits a cubo-octahedron of copper atoms mu(3)-bridged by (NPh)(2-) -ligands. The solid state structures of compounds 1-9 have been determined by single crystal X-ray diffraction. [References: 47]