Orto Peter J, Nichol Gary S, Wang Ruiyao, Zheng Zhiping
Department of Chemistry, University of Arizona, Tucson, Arizona 85721, USA.
Inorg Chem. 2007 Oct 15;46(21):8436-8. doi: 10.1021/ic700561q. Epub 2007 Sep 15.
The first Re(6)(mu(3)-Se)(8) core-containing cluster carbonyls, [Re(6)(mu(3)-Se)(8)(PEt(3))(5)(CO)]SbF(6) and trans-[Re(6)(mu(3)-Se)(8)(PEt(3))4(CO)(2)]SbF(6), were produced by reacting [Re(6)(mu(3)-Se)(8)(PEt(3))(5)I]I and trans-[Re(6)(mu(3)-Se)8(PEt(3))(4)I2], respectively, with AgSbF(6) in CO-saturated dichloromethane solutions. Spectroscopic and crystallographic studies suggest significant cluster-to-CO back-donation in these novel cluster derivatives and interesting electronic structures. Thermal and photolytic studies of the mono-carbonyl complex revealed its interesting and synthetically useful reactivity in producing new cluster derivatives.
首个含Re(6)(μ(3)-Se)(8)核心的簇状羰基化合物,即[Re(6)(μ(3)-Se)(8)(PEt(3))(5)(CO)]SbF(6)和反式-[Re(6)(μ(3)-Se)(8)(PEt(3))4(CO)(2)]SbF(6),分别通过使[Re(6)(μ(3)-Se)(8)(PEt(3))(5)I]I和反式-[Re(6)(μ(3)-Se)8(PEt(3))(4)I2]与AgSbF(6)在CO饱和的二氯甲烷溶液中反应制得。光谱学和晶体学研究表明,在这些新型簇状衍生物中存在显著的簇到CO的反馈π键作用以及有趣的电子结构。对单羰基配合物的热稳定性和光解研究揭示了其在生成新的簇状衍生物方面具有有趣且对合成有用的反应活性。