Transition metal benzyne complexes are organometallic complexes that contain benzyne ligands (C6H4). Unlike benzyne itself, these complexes are less reactive although they undergo a number of insertion reactions.[1]
The studies of metal-benzyne complexes were initiated with the preparation of zirconocene complex by reaction diphenylzirconocene with trimethylphosphine.[2]
Cp2ZrPh2 + PMe3 → Cp2Zr(C6H4)(PMe3) + PhH
The preparation of Ta(η5-C5Me5)(C6H4)Me2 proceeds similarly, requiring the phenyl complex Ta(η5-C5Me5)(C6H5)Me3. This complex is prepared by treatment of Ta(η5-C5Me5)Me3Cl with phenyllithium.[3] Upon heating, this complex eliminates methane, leaving the benzyne complex:
Ta(η5-C5Me5)(C6H5)Me3 → Ta(η5-C5Me5)(C6H4)Me2 + CH4
The second example of a benzyne complex is Ni(η2-C6H4)(dcpe) (dcpe = Cy2PCH2CH2PCy2). It is produced by dehalogenation of the bromophenyl complex NiCl(C6H4Br-2)(dcpe) with sodium amalgam. Its coordination geometry is close to trigonal planar.
Benzyne complexes react with a variety of electrophiles, resulting in insertion into one M-C bond. With trifluoroacetic acid, benzene is lost to give the trifluoroacetate Ni(O2CF3)2(dcpe).[4]
Several benzyne complexes have been examined by X-ray crystallography.
Bond | Ta | Ni | Zr | |
---|---|---|---|---|
M-C1 | 2.059 | 1.868 | 2.267 | |
M-C2 | 2.091 | 1.870 | 2.228 | |
C1-C2 | 1.364 | 1.332 | 1.364 | |
C2-C3 | 1.410 | 1.389 | 1.389 | |
C3-C4 | 1.362 | 1.383 | 1.383 | |
C4-C5 | 1.403 | 0.93 | 1.380 | |
C5-C6 | 1.375 | 1.383 | 1.377 | |
C6-C1 | 1.408 | 1.386 | 1.406 |
Angle | Ni | Zr | |
---|---|---|---|
1 | 41.9 | 35.3 | |
2 | 69.2 | 70.8 | |
3 | 69.1 | 73.9 | |
4 | 122.9 | 120.2 | |
5 | 122.3 | 122.1 | |
6 | 116.1 | (n/a) | |
7 | 121.5 | (n/a) | |
8 | 121.0 | (n/a) | |
9 | 116.2 | (n/a) |