STUDY ON STRUCTURES OF d10 METAL POLYNUCLEAR COMPLEXES. Xianglin Jin, Kaluo Tang and Youqi Tang, Institute of Physical Chemistry, Peking University, Beijing 100871, P. R. China
More than ten d10 metal (Cu,Ag,Cd) cluster complexes have been
synthesized by the insertion of carbon disulfide into M-S bonds and
structurally characterized by x-ray diffraction. We have found that silver and
copper thiolate complexes can react with CS2 in the presence of
PPh3 to give mononuclear insertion products, which can react easily
with various solvents to form unexpected polynuclear complexes, such as,
Cul4(u2-S)(SPh)12
(PPh3)6(l),
Agl4(u6-S)(SPh)l2(PPh3)8(),
(Ag5I6)n(Ph3PCH2I)n(3) and so on.
We also found some cadmium thiolate complexes react with CS2 in
organic solvents, resulting polynuclear complexes
(Me4N)2[SCd8(SPh)l2Cl4](4,
[Cd(H20)6]
[SCd8(SPh)l2Cl4](5),
[S4Cdl7(SPh)24(CH30CS2)
In complexes (1) or (2), there is a cage M14Sl2
(M=Cu,Ag) which is composed of staggered M6, M8 and
S12 polyhedra. The central S atom is essential for the formation of
Ml4 complexes, which might be the result of nucleophilic reaction of
PhS- and CS2. In complex (3), the polyanion
(Ag5I6)n is composed of alternate I6
pentagonal pyramids and Ag5 pentagons, which connected by Ag-I bonds
to form a layered "pagoda" structure. In complexes (4),(5) or (6),
u4-S atoms which also might be from the nucleophilic reaction of
PhS- and CS2 cement together Cd ions to form
Cd8 or Cd17 polynuclear complexes.