PREPARATION, CHARACTERIZATION, AND SOME PROPERTIES OF A T-CAGE-TYPE S-BRIDGED RH4(III)ZN3(II) HEPTANUCLEAR COMPLEX WITH A DEFECTIVE [ZN3HO](5+) CORE - CRYSTAL-STRUCTURE OF SPONTANEOUSLY RESOLVED [(RH(AET)(3))4ZN3HO]BR-5 (AET=2-AMINOETHANETHIOLATE)

The reaction of fac(S)-[Rh(aet)(3)] with ZnBr2 in water produced a T-cage-type S-bridged polynuclear complex with a ''defective'' [Zn3HO](5+) core, [{Rh(aet)(3)}4Zn3HO]Br-5 (1Br(5)), which was subject to spontaneous resolution to give (+)(350)(CD) and (-)(350)(CD) isomers. 1 was also optically resolved into the two isomers with use of [Sb-2(R,R-tartrate)(2)](2-). The crystal structure and absolute configuration for the spontaneously resolved (-)(350)(CD) isomer were determined by X-ray crystallography. [{Rh(C2H6NS)(3)}4Zn3HO]Br-5.9H(2)O, crystallizes in the cubic space group P2(1)3 with a=19.186 (1) Angstrom, V=7062.1 (4) Angstrom(3), Z=4, and R=0.0648. In 1 the four octahedral fac(S)-[Rh(aet)(3)] subunits are bound to a quasi-tetrahedral [Zn3HO](5+) core in a tetrahedral arrangement. The chiral configurations are regulated to Delta for all fac(S)-[Rh(aet)(3)] subunits and R for all asymmetric bridging sulfur atoms in (-)(350)(CD)-1, giving a quasi-T symmetrical structure. 1 is unstable in water and convertible to a T-cage-type octanuclear complex with a ''complete'' [Zn4O](6+) core, [{Rh(aet)(3)}4Zn4O](6+) (2), and to a linear-type S-bridged trinuclear complex, [Co{Rh(aet)(3)}(2)](3+), by adding ZnBr2 and [CoCl(NH3)(5)]Cl-2, respectively. The electronic absorption and circular dichroism (CD) spectral behavior of 1 are discussed in comparison with those of 2.