Facile access to the hydrazone functionalized PdGeS cluster [{R(N)Ge(mu-S)3}4Pd6] from the thiogermanate anion [{R(N)Ge}2(mu-S)2S2]2-.
The decanuclear ternary PdGeS cluster [{R(N)Ge(mu-S)(3)}(4)Pd(6)] x MeOH (2 x MeOH) has been obtained in high yield by a two-step reaction, involving the derivatization of the carbonyl functionalized adamantane-like [(R(1)Ge)(4)(mu-S)(6)] (R(1) = CMe(2)CH(2)COMe) with N(2)H(4) x H(2)O, and a subsequent reaction of the resulting hydrazone functionalized thiogermanate (NH(3)NH(2))(2)[(R(N)Ge)(2)(mu-S)(2)S(2)] (R(N) = CMe(2)CH(2)CMeNNH(2), 1) with an acidic solution of (N,N'-tmeda)Pd(NO(3))(2). Cluster 2 has an elegant molecular structure which can be viewed as an R(N) ligated ensemble of four edge-sharing [Pd(3)GeS(3)] defect hetercubanes that meet at an unoccupied center. Thus, the cluster consists of six square-planar coordinated Pd(II) ions at the vertices of a regular octahedron with four faces capped by four [R(N)GeS(3)](3-) units. The title compounds were structurally characterized by means of single-crystal X-ray diffraction as well as physical property measurements. Moreover, density functional theory calculations were performed to gain insight into the unique coordination situation of the hydrazone substituent.
Halvagar
Mohammad Reza
MR
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, 35043 Marburg, Germany.
Hassanzadeh Fard
Zohreh
Z
Xiong
Lin
L
Dehnen
Stefanie
S