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Synthesis, reactions and structure of bromo(η5-diphenylphosphinylcyclopentadienyl)nickel(II) dimer

Journal of Organometallic Chemistry
Publication Date
DOI: 10.1016/s0022-328x(99)00429-5
  • Diphenylphosphinylcyclopentadienyl
  • Nickel
  • Homobimetallic
  • X-Ray Diffraction


Abstract The reaction of diphenylphosphinylcyclopentadienylthallium ( 1) with NiBr 2·2DME has produced Ni 2(η 5-C 5H 4PPh 2) 2Br 2 ( 2) in quantitative yield. A reaction of 2 with methyl-lithium affords Ni 2(η 5-C 5H 4PPh 2) 2(CH 3) 2 ( 3) in high yield. Both 2·0.5CH 2Cl 2 and 3 have been characterized by means of single crystal X-ray diffraction studies and shown to be homobimetallic, with cyclic dimeric structures. Each ligand bridges two metal centers via P coordination to one and η 5-coordination of the cyclopentadienyl moiety to a second Ni 2+. Each nickel atom is thus formally five-coordinate with average bonding parameters of Ni–Centroid (Cp), Ni–P, and Ni–X of 1.760(5), 2.154(5), Br: 2.301(8) Å ( 2) and 1.769(5), 2.113(5), CH 3: 1.944(1) Å ( 3). The P–Ni–X angles are compressed in 3 compared to 2 by an average of 4°.

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