n(2)-Coordination of a Phosphaalkyne to an Amino Olefin Nickel Complex and Regioselective Catalyzed Cyclooligomerization to Dewar 1,3,5-Triphosphabenzene

作者：Trincado, Monica^*; Rosenthal, Amos J; Vogt, Matthias; Gruetzmacher, Hansjoerg

来源：European Journal of Inorganic Chemistry, 2014, 2014(10): 1599-1604.

DOI：10.1002/ejic.201301135

• Nickel
• Phosphaalkynes
• Cyclooligomerization
• Coordination modes
• Alkene ligands

We report herein an efficient synthesis of a Dewar-triphosphabenzene derived from [2 2 2] cycloaddition of three phosphaalkyne molecules promoted by an amino olefin Ni-0 complex as the catalyst. Amino diolefin Ni-I complex 1 serves as a precursor complex that reacts with triphenylmethylphosphaethyne under reducing conditions at low temperature to give Ni-0 complex 3 with a coordinated phosphaalkyne in a (2)-mode. The structure of 3 was determined by X-ray diffraction methods and suggests a bonding situation for the phosphaalkyne that is between a side-on coordinated CP molecule and a metallaphosphacyclopropene structure. The reaction of 3 with a 10-fold excess of phosphaethylene under reducing conditions at room temperature resulted in the formation of 2,4,6-tris(triphenylmethyl)-Dewar-1,3,5-triphosphabenzene (4) in good yield.

• 出版日期2014-4
• 单位中山大学