Kuhlman Matthew L, Rauchfuss Thomas B
Department of Chemistry, University of Illinois at Urbana--Champaign, Urbana, Illinois 61801, USA.
Inorg Chem. 2004 Jan 26;43(2):430-5. doi: 10.1021/ic034745s.
Condensation of cyanometalates and cluster building blocks leads to the formation of hybrid molecular cyanometalate cages. Specifically, the reaction of [Cs subset CpCo(CN)(3)CpRu] and [(cymene)(2)Ru(3)S(2)(NCMe)(3)]PF(6) produced Cs subset CpCo(CN)(3)[(cymene)(2)Ru(3)S(2)]CpRu(2), Cs subset Co(4)Ru(6)S(2)(2+). Single-crystal X-ray diffraction, NMR spectroscopy, and ESI-MS measurements show that Cs subset Co(4)Ru(6)S(2)(2+ ) consists of a Ru(4)Co(4)(CN)(12) box fused with a Ru(3)S(2) cluster via a common Ru atom. The reaction of PPN[CpCo(CN)(3)] and 0.75 equiv of (cymene)(2)(MeCN)(3)Ru(3)S(2)(2) in MeCN solution produced CpCo(CN)(3)(cymene)(2)Ru(3)S(2)(2), Co(4)Ru(9)S(6)(2+). Crystallographic analysis, together with NMR and ESI-MS measurements, shows that Co(4)Ru(9)S(6)(2+ ) consists of a Ru(3)Co(4)(CN)(9) "defect box" core, wherein each Ru is fused to a Ru(3)S(2) clusters. The analogous condensation using CpRh(CN)(3) in place of CpCo(CN)(3) produced the related cluster-cage Rh(4)Ru(9)S(6)(2+). Electrochemical analyses of both Co(4)Ru(9)S(6)(2+) and Rh(4)Ru(9)S(6)(2+) can be rationalized in the context of reduction at the cluster and the Co(III) subunits, the latter being affected by the presence of alkali metal cations.
氰基金属酸盐与簇状结构单元的缩合反应导致了杂化分子氰基金属酸盐笼的形成。具体而言，[Cs subset CpCo(CN)(3)CpRu]与[(cymene)(2)Ru(3)S(2)(NCMe)(3)]PF(6)反应生成了Cs subset CpCo(CN)(3)[(cymene)(2)Ru(3)S(2)]CpRu(2)，即Cs subset Co(4)Ru(6)S(2)(2+)。单晶X射线衍射、核磁共振光谱和电喷雾电离质谱测量结果表明，Cs subset Co(4)Ru(6)S(2)(2+)由一个Ru(4)Co(4)(CN)(12)盒与一个通过一个共用Ru原子连接的Ru(3)S(2)簇融合而成。PPN[CpCo(CN)(3)]与0.75当量的(cymene)(2)(MeCN)(3)Ru(3)S(2)(2)在乙腈溶液中反应生成了CpCo(CN)(3)(cymene)(2)Ru(3)S(2)(2)，即Co(4)Ru(9)S(6)(2+)。晶体学分析以及核磁共振和电喷雾电离质谱测量结果表明，Co(4)Ru(9)S(6)(2+)由一个Ru(3)Co(4)(CN)(9)“缺陷盒”核心组成，其中每个Ru与一个Ru(3)S(2)簇融合。使用CpRh(CN)(3)代替CpCo(CN)(3)进行类似的缩合反应生成了相关的簇-笼Rh(4)Ru(9)S(6)(2+)。Co(4)Ru(9)S(6)(2+)和Rh(4)Ru(9)S(6)(2+)的电化学分析可以在簇和Co(III)亚单元还原的背景下得到合理解释，后者受碱金属阳离子存在的影响。
