Pyridine-based SNS-iridium and -rhodium sulfide complexes, including d8-d8 metal-metal interactions in the solid state.
Pyridine-based SNS-iridium and -rhodium sulfide complexes, including d8-d8 metal-metal interactions in the solid state.
复制标题
基于吡啶的 SNS-铱和硫化铑络合物，包括固态下的 d8-d8 金属-金属相互作用。
DOI：
10.1039/b802223b
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发表时间：
2008
影响因子：
4
通讯作者：
D. Milstein
中科院分区：
文献类型：
--
作者：
Yulie Klerman;Eyal Ben;Y. Diskin‐Posner;G. Leitus;L. Shimon;Yehoshoa Ben‐David;D. Milstein
合成了阳离子钳形配合物[（SNS）Ir（COE）][BF_4]（1）和[（SNS）Rh（COE）][BF_4]（2）（SNS = 2，6-二（叔丁基硫甲基）吡啶; COE =环辛烯），并研究了它们的结构和反应性能。它们在室温下是流动的，这是由于“臂”的半不稳定性，它可以在低温下冻结。配合物1与H2反应生成二聚二氢化物配合物[（SNS）Ir（H2）]2[BF 4]2（3），其中硫原子桥接在两个金属中心之间。Rh配合物2不与H2反应。两种羰基配合物[（SNS）Ir（CO）][BF 4]（5）和[（SNS）Rh（CO）][BF 4]（6）在溶液与固体状态中显示出IR伸缩频率的差异，这是固态中正方形平面d8系统之间的不常见的金属-金属相互作用的结果。配合物1、3、5和6的结构经X-射线晶体学表征。配合物5中的氢原子与BF_4（-）抗衡阴离子形成了氢键网络。
The cationic, pincer-type complexes [(SNS)Ir(COE)][BF4] (1) and [(SNS)Rh(COE)][BF4] (2) (SNS = 2,6-bis(t-butylthiomethy1)pyridine; COE = cyclooctene) complexes were prepared, and their structure and reactivity were studied. They are fluxional at room temperature as a result of "arm" hemilability, which can be frozen at low temperatures. Reaction of complex 1 with H2 resulted in a dimeric dihydride complex [(SNS)Ir(H2)]2[BF4]2 (3) in which the sulfur atoms bridge between two metal centers. The Rh complex 2 did not react with H2. Both the carbonyl complexes [(SNS)Ir(CO)][BF4] (5) and [(SNS)Rh(CO)][BF4] (6) show differences in the IR stretching frequencies in solution vs. solid states, which are a result of uncommon metal-metal interactions between square planar d8 systems in the solid state. Complexes 1, 3, 5 and 6 were structurally characterized by X-ray crystallography. A network of hydrogen bonds involving the BF4(-) counter anion and hydrogen atoms of complex 5 was observed.