Synthesis of a Sulfido- and Thiolato-Bridged Trinuclear Bimetallic Cluster [{(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ir}<sub>2</sub>{(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Ru}Cl(μ<sub>3</sub>-S)(μ<sub>2</sub>-SCH<sub>2</sub>CH<sub>2</sub>CN)<sub>2</sub>] and Its Reactions with CO, Isocyanide, and Alkyne
收藏NIAID Data Ecosystem2026-03-06 收录
下载链接：
https://figshare.com/articles/dataset/Synthesis_of_a_Sulfido_and_Thiolato_Bridged_Trinuclear_Bimetallic_Cluster_sup_5_sup_C_sub_5_sub_Me_sub_5_sub_Ir_sub_2_sub_sup_5_sup_C_sub_5_sub_H_sub_5_sub_Ru_Cl_sub_3_sub_S_sub_2_sub_SCH_sub_2_sub_CH_sub_2_sub_CN_sub_2_sub_and_Its_Reactions_with_CO_Isocy/3253543
下载链接
链接失效反馈官方服务：
资源简介：
Treatment of a sulfido- and thiolato-bridged diiridium complex [(Cp*Ir)2(μ-S)(μ-SCH2CH2CN)2] (3; Cp* = η5-C5Me5) with [CpRuCl(tmeda)] (Cp = η5-C5H5; tmeda = N,N,N‘,N‘-tetramethylethylenediamine) gave the Ir2Ru sulfido-thiolato cluster [(Cp*Ir)2(CpRu)Cl(μ3-S)(μ2-SCH2CH2CN)2] (4), the core structure of which is the same as that of the previously
reported Cp*Ru analogue [(Cp*Ir)2(Cp*Ru)Cl(μ3-S)(μ2-SCH2CH2CN)2] (2), but the geometry
around one Ir atom and the orientation of the cyanoethyl group in one thiolato ligand differ
from those in 2. Cluster 4 reacted with L (L = CO and XyNC; Xy = 2,6-Me2C6H3) in the
presence of KPF6 to afford [(Cp*Ir)2(CpRu)(L)(μ3-S)(μ2-SCH2CH2CN)2][PF6] (5), in which the
ligand L is bonded to one Ir center in a terminal end-on fashion. On the other hand, the
reaction of 4 with MeOCOC⋮CCOOMe (DMAD) resulted in the insertion of DMAD into the
Ru−Ssulfido bond, yielding the cluster [(Cp*Ir)2(CpRu){μ3-SC(COOMe)CCOOMe}(μ2-SCH2CH2CN)2][PF6] (6). In 6, the DMAD molecule bridges the Ru and μ2-S atoms, and the resulting
CC bond in the DMAD moiety further coordinates to one Ir atom in a side-on manner. To
confirm the difference in the reactivities toward alkynes between the Ir sites in 4 and 2,
reaction of DMAD with 2 was carried out, which resulted in the formation of the
alkenylthiolato cluster [(Cp*Ir)2(Cp*Ru)(μ3-S){μ3-SC(COOMe)CHCOOMe}(μ2-SCH2CH2CN)][PF6] (8) containing the DMAD moiety bonded to the two Ir atoms. Cluster 6 dissolved in
MeCN reacted further with CO (10 atm) at 80 °C and XyNC at 60 °C to give [(Cp*Ir)2(CpRu)(L){μ3-SC(COOMe)CCOOMe}(μ2-SCH2CH2CN)2][PF6] (9), where the migration of
the DMAD moiety occurred to form the iridathiacyclobutene moiety, accompanied by the
coordination of L to the other Ir site. The X-ray analyses have been undertaken to determine
the detailed structures for five new clusters: 4, the BPh4 analogue of 5b (L = XyNC) [(Cp*Ir)2(CpRu)(XyNC)(μ3-S)(μ2-SCH2CH2CN)2][BPh4], 6, 8, and 9b (L = XyNC).
创建时间：
2016-05-05
