Removing a second mercury atom from [Os18Hg3C2(CO)42]2–: synthesis of [Os18HgC2(CO)42]4–and crystal structure of [PPh3H]3[Os18HgHC2(CO)42]
摘要:
Upon reduction of [N(PPh(3))(2)](2)[Os18HgxC2(CO)(42)] (x = 2 or 3) with sodium diphenylketyl in tetrahydrofuran a hexaanionic cluster, [Os18HgxC2(CO)(42)](6-), is generated which could only be partially characterised by IR spectroscopy as well as through its chemical reactivity. After chromatographic work-up the tetraanionic cluster [Os18HgC2(CO)(42)](4-) was isolated as the exclusive reaction product. This was also obtained in low yield (20-30%) by thermolytic degradation of [Os18Hg2C2(CO)(42)](2-) in CH2CI2. As a consequence of traces of HCl in the CH2CI2 as well as degradation of the cation, the salt [PPh(3)H](3)[Os18Hg2HC2(CO)(42)] crystallised from the reaction mixture. An X-ray single-crystal analysis of the latter has established its solid-state structure in which two Os9C units are u(6)-linked by a central mercury atom. The [Os18HgC2(CO)(42)](4-) cluster may be converted into the dimercury cluster dianion [Os18Hg2C2(CO)(42)](2-) by reaction with Hg(O3SCF3)(2).
Routes to high-nuclearity mixed-metal clusters; the synthesis and X-ray structure analysis of the [N(PPh<sub>3</sub>)<sub>2</sub>]<sup>+</sup>salts of [Os<sub>10</sub>C(CO)<sub>24</sub>AuBr]<sup>–</sup>, [Os<sub>20</sub>Au(C)<sub>2</sub>(CO)<sub>48</sub>]<sup>2–</sup>, and [Os<sub>20</sub>Hg(C)<sub>2</sub>(CO)<sub>48</sub>]<sup>2–</sup>
作者:Simon R. Drake、Kim Henrick、Brian F. G. Johnson、Jack Lewis、Mary McPartlin、Jill Morris
DOI:10.1039/c39860000928
日期:——
The large anionic clusters [Os20M(C)2(CO)24]2–(M = Au or Hg) have been prepared from the dianion [Os10C(CO)24]2–, and their metal framework structures and the overall structures of [Os10C(CO)24AuBr]–, an intermediate in the formation of the gold compound, have been established by X-ray single crystal analyses.