Blankenship Trevor V, Dickman Matthew J, van de Burgt Lambertus J, Latturner Susan E
Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306, United States.
Inorg Chem. 2015 Feb 2;54(3):914-21. doi: 10.1021/ic502315m. Epub 2014 Nov 6.
Two new complex main-group metal carbides were synthesized from reactions of indium, carbon, and a metal hydride in metal flux mixtures of an alkaline earth (AE = Ca, Ba) and lithium. Ca(12)InC(13-x) and Ba(12)InC(18)H(4) both crystallize in cubic space group Im3̅ [a = 9.6055(8) and 11.1447(7) Å, respectively]. Their related structures are both built on a body-centered-cubic array of icosahedral clusters comprised of an indium atom and 12 surrounding alkaline-earth cations; these clusters are connected by bridging monatomic anions (either H(-) or C(4-)) and allenylide anions, C(3)(4-). The allenylide anions were characterized by Raman spectroscopy and hydrolysis studies. Density of states and crystal orbital Hamilton population calculations confirm that both compounds are metallic.
通过铟、碳与金属氢化物在碱土金属（AE = Ca、Ba）和锂的金属助熔剂混合物中反应，合成了两种新型的复杂主族金属碳化物。Ca(12)InC(13 - x)和Ba(12)InC(18)H(4)均结晶于立方空间群Im3̅ [a分别为9.6055(8) Å和11.1447(7) Å]。它们的相关结构均基于由一个铟原子和12个周围的碱土金属阳离子组成的二十面体簇的体心立方阵列构建而成；这些簇通过桥连单原子阴离子（H⁻或C⁴⁻）和丙二烯基阴离子C₃⁴⁻相连。通过拉曼光谱和水解研究对丙二烯基阴离子进行了表征。态密度和晶体轨道哈密顿布居计算证实这两种化合物均为金属性。
