Transition metal benzyne complex explained

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]

Examples

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.

Reactivity

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]

Structural trends

Several benzyne complexes have been examined by X-ray crystallography.

Bond lengths (Å) in Ta, Ni and Zr benzyne complexes
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

Bond angles (degrees) in Ni and Zr benzyne complexes
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)

Notes and References

  1. Buchwald, S. L.; Nielsen, R. B. "Group 4 Metal Complexes of Benzynes, Cycloalkynes, Acyclic Alkynes, and Alkenes" Chem. Rev. 1988, volume 88, 1047-1058
  2. Buchwald, S. L.; Watson, B. T. The Trimethylphosphine Adduct of the Zirconocene-Benzyne Complex: Synthesis, Reactions, and X-ray Crystal Structure. J. Am. Chem. Soc. 1986, 108, 7411-7413
  3. McLain, S. J.; Schrock, R. R.; Sharp, P. R.; Churchill, M. R.; Youngs, W. J. Synthesis of Monomeric Niobium- and Tantalum-Benzyne Complexes and Molecular Structure of Ta(η5-C5Me5)(C6H4)Me2" J. Am. Chem. Soc. 1979, volume 101, 263-265
  4. Bennett, M. A. . Hambley, T. W. . Roberts, N. K. . Robertson, G. B. . Synthesis and Single-Crystal X-ray Study of the Mononuclear η2-Benzyne (Dehydrobenzene) Nickel(0) Complex Ni(η2-C6H4)((C6H11)2PCH2CH2P(C6H11)2). Insertion Reactions with Simple Molecules and X-ray Crystal Structure of the Nickelaidan Complex Ni(CH2CH2C6H4-o)((C6H11)2PCH2CH2P(C6H11)2)" . Organometallics. 1985. 4. 1992–2000. 10.1021/om00130a012.