217320-18-8Relevant academic research and scientific papers
Reaction of (σ-alkynyl) Group 4 metallocene cation complexes with alkyl- and arylisocyanides
Ahlers, Wolfgang,Erker, Gerhard,Froehlich, Roland
, p. 83 - 89 (1998)
The cations [(RCp)2M(-CC-CH3)(THF)+] (2a-d) [(RCp)2M=Cp2Ti, Cp2Zr, (MeCp)2Zr, and Cp2Hf] were generated in situ by treatment of the respective bis(propynyl) Group 4 metallocenes (RCp)2M(-CC-CH3)2 (1a-d) with N,N-dimethylanilinium tetraphenylborate. Addition of excess tert-butylisocyanide gave the isonitrile insertion/addition products [(RCp)2M(η2-Me3C-NC-CC-CH 3)(κ-CN-CMe3)+] (8a-d). Complex 8b was characterized by X-ray diffraction. It contains a η2-iminoacyl ligand with N-inside orientation and there is a κ-tert-butylisocyanide coordinated to the cationic metallocene framework. Complex 8b exhibits the typical structural characteristics of a do-configurated isonitrile complex (bond lengths 2.350(4) and 1.148(4) A for the Zr-CN-R unit). Insertion of 2,6-dimethylphenylisocyanide into the Zr-C(sp) σ-bond of in situ generated [Cp2Hf-CC-CH3+] cation 2d leads to the formation of the analogous cationic hafnocene complex 8e.
