M-S vibrational study in three-coordinate thiolato compounds (NEt4)2[M(SC6H4-p-X)3] and (NEt4)2[M4(μ-SC6H4-p-Cl)6]:: M=Cu(I) and Ag(I), X=Cl and Br

By using p-substituted benzenethiolate ligands, the novel three-coordinate copper(I) and silver(I) thiolato complexes (NEt4)(2)[Cu(SC6H4-p-X)(3)] (X=Cl (1) and Br (2)), (NEt4)(2)[Ag(SC6H4-p-X)(3)] (X=Cl (3) and Br (4)) and novel clusters (NEt4)(2)L-2[M-4(mu -SC6H4-p-Cl)(6)] (M=Cu (5) and Ag(6)) have been prepared and structurally characterized by single crystal X-ray diffraction. All the complexes have three-coordinate sites having point-group D-3h symmetry. The three-coordinate mononuclear silver(I) complexes 3 and 4 are the first examples. The M-S stretching bands were determined by far-IR and FT-Raman spectroscopies; nu (Cu-S) 363-372 cm(-1) and nu (Ag-S) 353-363 cm(-1). These results indicate that M-S stretching vibration energy in the three-coordinate metal(I) site of the mononuclear compounds or clusters is around 340-380 cm(-1), and it is a useful tool for determining their coordination modes. (C) 2000 Elsevier Science B.V. All rights reserved.