1342285-52-2Relevant academic research and scientific papers
The impact of P-substituents on the structures, spectroscopic properties, and reactivities of POCOP-type pincer complexes of nickel(II)
Salah, Abderrahmen B.,Zargarian, Davit
, p. 8977 - 8985 (2011/10/12)
The room temperature reaction of NiBr2(NCCH3) x with the pincer-type ligand POCHOPPh gave the new pincer complex (POCOPPh)NiBr (1, POCOPPh = κP, κC, κP-2,6-{Ph2PO} 2C6H3). Complex 1 reacts with AgX to give the analogous Ni-X derivatives (X = CN, 2; OSO2CF3, 3; OC(O)CH3, 4; ONO2, 5), whereas complex 3 reacts with phenylacetylene and NEt3 to give the Ni-CCPh derivative 6. On the other hand, reaction of 1 or 3 with RLi or RMgI did not afford the desired Ni-R derivatives, giving instead the corresponding iodo and hydroxo derivatives. Complexes 1-6 have been characterized by NMR, IR, and UV-Vis spectroscopy and X-ray crystallography. The solid state structural and IR data indicate that Ni-Csp interaction is dominated by ligand-to-metal σ-donation in 2 and 6. Cyclic voltammetry measurements indicate that complexes 3 and 4 display reversible redox behaviour (NiII/NiIII); comparison of the E01/2 values for these complexes and their POCOPi-Pr analogues shows that both the X ligands and the P-substituent have a considerable impact on the ease of oxidation in this family of complexes. The Royal Society of Chemistry 2011.
