Wu De-Hong, Wu Chun-Hui, Li Yi-Zhi, Guo Da-Dong, Wang Xue-Mei, Yan Hong
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210093, China.
Dalton Trans. 2009 Jan 14(2):285-90. doi: 10.1039/b810831e. Epub 2008 Nov 10.
The addition reactions of the 16e half-sandwich complexes (p-cymene)M(S2C2B10H10) (, M=Ru; , M=Os) and CpIr(E2C2B10H10) (, E=S; , E=Se) with ethynylferrocene lead selectively to the 18e complexes (p-cymene)Ru(S2C2B10H9)(H2CCFc) (Fc=ferrocenyl) (), (p-cymene)Os(S2C2B10H9)(H2CCFc) (), CpIr(S2C2B10H9)(H2CCFc) () and Cp*Ir(Se2C2B10H9)(H2CCFc) (), in which the alkyne is regio- and stereoselectively inserted into one of the M-E bonds that may further lead to metal-induced B-H activation, hydrogen atom transfer from the carborane via the metal center to the inserted alkyne, and the generation of a M-B bond. In all complexes the S-eta2-(Fc)C-C and C-B(M) moieties occupy a cisoid position. The four new complexes are characterized by IR, MS, NMR spectroscopy and microanalysis, and the X-ray structural analysis of is performed. was observed to promote the uptake of anticancer drug daunorubicin in drug-resistant leukemia K562 cells.
16电子半夹心配合物（对异丙基苯）M（S₂C₂B₁₀H₁₀）（M = Ru； ，M = Os）和CpIr（E₂C₂B₁₀H₁₀）（E = S； ，E = Se）与乙炔基二茂铁的加成反应选择性地生成18电子配合物（对异丙基苯）Ru（S₂C₂B₁₀H₉）（H₂CCFc）（Fc = 二茂铁基）（ ）、（对异丙基苯）Os（S₂C₂B₁₀H₉）（H₂CCFc）（ ）、CpIr（S₂C₂B₁₀H₉）（H₂CCFc）（ ）和Cp*Ir（Se₂C₂B₁₀H₉）（H₂CCFc）（ ），其中炔烃区域和立体选择性地插入到一个M - E键中，这可能进一步导致金属诱导的B - H活化、氢原子从碳硼烷经金属中心转移到插入的炔烃上，并生成M - B键。在所有配合物中，S-η²-（Fc）C - C和C - B（M）部分处于顺式位置。这四种新配合物通过红外光谱、质谱、核磁共振光谱和微量分析进行表征，并对 进行了X射线结构分析。观察到 可促进耐药白血病K562细胞对抗癌药物柔红霉素的摄取。
