Synthesis and characterization of fluorophenylpalladium pincer complexes: electronic properties of some pincer ligands evaluated by multinuclear NMR spectroscopy and electrochemical studies

Alexey V Polukeev; Sergey A Kuklin; Pavel V Petrovskii; Svetlana M Peregudova; Alexander F Smol'yakov; Fedor M Dolgushin; Avthandil A Koridze

doi:10.1039/c1dt10446b

Synthesis and characterization of fluorophenylpalladium pincer complexes: electronic properties of some pincer ligands evaluated by multinuclear NMR spectroscopy and electrochemical studies

Dalton Trans. 2011 Jul 21;40(27):7201-9. doi: 10.1039/c1dt10446b. Epub 2011 Jun 10.

Authors

Alexey V Polukeev¹, Sergey A Kuklin, Pavel V Petrovskii, Svetlana M Peregudova, Alexander F Smol'yakov, Fedor M Dolgushin, Avthandil A Koridze

Affiliation

¹ A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, 119991, Moscow, Russian Federation.

PMID: 21660346
DOI: 10.1039/c1dt10446b

Abstract

Palladium fluorophenyl complexes with different pincer ligands Pd(Ar)[2,6-(tBu(2)PCH(2))(2)C(6)H(3)] (13), Pd(Ar)[2,6-(tBu(2)PO)(2)C(6)H(3)] (14), Pd(Ar)[{2,5-(tBu(2)PCH(2))(2)C(5)H(2)}Fe(C(5)H(5))] (15), and Pd(Ar)[{2,5-(tBu(2)PCH(2))(2)C(5)H(2)}Ru(C(5)H(5))] (16) were synthesized by the reaction of LiAr (Ar = C(6)H(4)F-4) with the respective trifluoroacetate palladium pincer complexes 9-12. The molecular structures of 14 and 16 were determined by an X-ray crystallographic method. Complexes 13-16 and {Pd(Ar)[{2,5-(tBu(2)PCH(2))(2)C(5)H(2)}Fe(C(5)H(5))]}PF(6) (17) were studied by multinuclear NMR spectroscopy and cyclic voltammetry. On the basis of (19)F NMR chemical shifts and (1)J((13)C-(19)F) coupling constants, as well as Pd(II)/Pd(IV) oxidation potentials, electronic characteristics of the corresponding pincer ligands were elucidated.