The studies of metal-benzyne complexes were initiated with the preparation of zirconocene complex by reaction diphenylzirconocene with trimethylphosphine. 
:CpZrPh + PMe → CpZr(CH)(PMe) + PhH
The preparation of Ta(η-CMe)(CH)Me proceeds similarly, requiring the phenyl complex Ta(η-CMe)(CH)Me. This complex is prepared by treatment of Ta(η-CMe)MeCl with phenyllithium. Upon heating, this complex eliminates methane, leaving the benzyne complex:
:Ta(η-CMe)(CH)Me → Ta(η-CMe)(CH)Me + CH
The second example of a benzyne complex is Ni(η-CH)(dcpe) (dcpe = CyPCHCHPCy). It is produced by dehalogenation of the bromophenyl complex NiCl(CHBr-2)(dcpe) with sodium amalgam. Its coordination geometry is close to trigonal planar.