Synthesis, structures and reactions of doubly bridged biscyclopentadienyl diruthenium complexes (CR₂)(EMe₂)[(畏⁵-C₅H₃)Ru(CO)₂]₂ (R聽=聽Me, H; E聽=聽Si, Ge)

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• 作者：Bolin Zhu^a ; ^{bolinzhu@yahoo.com.cn} ; Shansheng Xu^b ; Xiuzhong Zhou^b ; Baiquan Wang^b ; ^{bqwang@nankai.edu.cn}
• 关键词：Ru&ndash ; Ru bond ; Photolysis ; Halogen-bridged ; Doubly bridged biscyclopentadienyl ligand ; X-ray diffraction
• 刊名：Journal of Organometallic Chemistry
• 出版年：2012
• 期刊代码：64_0022328x
• 类别：ch
• 出版时间：15 June, 2012
• 卷：708-709
• 期：Complete
• 页码：88-97
• 文件大小：1101 K

摘要

Doubly bridged biscyclopentadienyl diruthenium complexes (CR₂)(EMe₂)[(畏⁵-C₅H₃)Ru(CO)₂]₂ (R聽=聽Me, E聽=聽Si (2), Ge (5); R聽=聽H, E聽=聽Si (7), Ge (10)) were synthesized, and fully characterized by ¹H NMR, IR, EA and single crystal X-ray diffraction. Due to the rigid double-bridged biscyclopentadienyl ligands and the long Ru-Ru bonds in their structures, a series of reactions about (CMe₂)(SiMe₂)[(畏⁵-C₅H₃)Ru(CO)₂]₂ (2), as a representative for this type of complexes, were carried out: 2 reacted with halogens to give unexpected halogen-bridged products (CMe₂)(SiMe₂)[(畏⁵-C₅H₃)₂Ru₂(CO)₃(X)](渭-X) (X聽=聽I (12), or Br (14)), in addition to the normal Ru-Ru-cleaved compounds (CMe₂)(SiMe₂)[(畏⁵-C₅H₃)Ru(CO)₂X]₂ (X聽=聽I (11), or Br (13)); UV photolysis of 2 with PPh₃ resulted in loss of two carbon monoxide ligands and P-C insertion by ruthenium to yield the complex (CMe₂)(SiMe₂)[(畏⁵-C₅H₃)₂Ru₂(CO)₂(蟽-Ph)][渭-PPh₂] (15); with C₂Ph₂ yielded [(CMe₂)(SiMe₂)(畏⁵-C₅H₃)₂]Ru₂(CO)[畏²:畏⁴-渭₂-C(Ph)C(Ph)C(Ph)C(Ph)] (16). Reactivity of doubly bridged ruthenium complex 2 with the respective non-bridged and singly bridged analogues was compared. The molecular structures of 12, 15 and 16 were also determined by X-ray diffraction.