有机化学 ›› 2013, Vol. 33 ›› Issue (08): 1697-1708.DOI: 10.6023/cjoc201305046 上一篇    下一篇

研究论文

一些锇烯基卡拜配合物的合成及其金属有机化学性质研究

安冉, 李亭, 温庭斌   

  1. 厦门大学化学化工学院化学系 厦门 361005
  • 收稿日期:2013-05-27 修回日期:2013-05-31 发布日期:2013-06-04
  • 通讯作者: 温庭斌 E-mail:chwtb@xmu.edu.cn
  • 基金资助:

    国家自然科学基金(No. 21072161);国家重点基础研究发展计划(973计划,No. 2012CB821600)及长江学者和创新团队发展计划资助项目.

Synthesis and Organometallic Properties of Several Osmium Alkenylcarbyne Complexes

An Ran, Li Ting, Wen Ting-Bin   

  1. Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005
  • Received:2013-05-27 Revised:2013-05-31 Published:2013-06-04
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21072161), the National Basic Research Program of China (973 Program, No. 2012CB821600), the Program for Changjiang Scholars and the Innovative Research Team in University (PCSIRT).

OsH2Cl2(PCy3)2 (1)与炔丙醇HC≡CC(OH)Ph2在室温及加热条件下反应可分别生成原子氢配位的γ-羟基卡拜配合物OsHCl2[≡CCH2C(OH)Ph2](PCy3)2 (2)和原子氢配位的烯基卡拜OsHCl2(≡CCH=CPh2)(PCy3)2 (3). 23在氯化氢乙醚溶液作用下可转化为三氯配位的烯基卡拜OsCl3(≡CCH=CPh2)(PCy3)2 (4). 也可通过OsH2Cl2(PCy3)2与HC≡CC(OH)Ph2在氯化氢乙醚溶液存在下反应, 由一锅法直接合成烯基卡拜配合物4. 化合物4还可通过OsCl3(≡CCH=CPh2)(PPh3)2 (5) 与PCy3的配体取代反应来制备, 在反应过程中可分离到单个PPh3配体被PCy3取代的产物OsCl3(≡CCH=CPh2)(PCy3)(PPh3) (6). 化合物4可与水及吡啶发生配体取代反应, 分别生成水或吡啶配位的单膦卡拜配合物OsCl3(≡CCH=CPh2)(PCy3)(S) (S=H2O, 7; S=Py, 8). 此外, 4与NaOEt在室温下反应可得到锇烯基卡宾配合物OsCl2(=CHCH=CPh2)(PCy3)2 (9), 而与EtOH需在加热条件下才可反应, 生成的是原子氢卡拜3. 化合物9在溶液中不稳定, 可完全转化为热力学稳定的原子氢配位的卡拜3.

关键词: 锇, 卡拜, 卡宾, 端基炔烃, 原子氢配合物

Reactions of the dihydride complex OsH2Cl2(PCy3)2 (1) with HC≡CC(OH)Ph2 at room temperature or under heating condition produce the hydride hydroxycarbyne complex OsHCl2[≡CCH2C(OH)Ph2](PCy3)2 (2) and the hydride alkenylcarbyne complex OsHCl2(≡CCH=CPh2)(PCy3)2 (3), respectively. Treatment of 2 or 3 with HCl·Et2O affords the trichlorocarbyne complex OsCl3(≡CCH=CPh2)(PCy3)2 (4), which can be conveniently synthesized by the one pot reaction of 1 with HC≡CC(OH)Ph2 in the presence of HCl·Et2O. Complex 4 can be alternatively prepared from the phosphine ligand substitution of the trichlorocarbyne complex OsCl3(≡CCH=CPh2)(PPh3)2 (5) with PCy3, from which the mono-substituted intermediate OsCl3(≡CCH=CPh2)(PCy3)(PPh3) (6) can be isolated. Complex 4 undergoes ligand substitution reactions with water and pyridine leading to the formation of the aqua and pyridine-coordinate mono phosphine carbyne complexes OsCl3(≡CCH=CPh2)(PCy3)(S) (S=H2O, 7; S=Py, 8). In addition, complex 4 reacts with NaOEt at room temperature to produce the alkenylcarbene complex OsCl2(=CHCH=CPh2)(PCy3)2 (9), which is unstable in solution and evolves into the thermally more stable hydride carbyne complex 3. In contrast, the reaction of 4 with EtOH can only take place at elevated temperature to give the hydride carbyne 3.

Key words: osmium, carbyne, carbene, terminal alkyne, hydride complex