期刊
INORGANICA CHIMICA ACTA
卷 512, 期 -, 页码 -出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2020.119862
关键词
Phosphanylquinoline; Trans in fluence; Tetrahedral distortion; Fluxional behavior; Racemization
资金
- JSPS KAKENHI Grant [18K05146]
- Grants-in-Aid for Scientific Research [18K05146] Funding Source: KAKEN
A series of cyclometalated {2-(2'-pyridyl)phenyl}platinum(II) complexes having 8-quinolylphosphines, 8-(dimethylphosphino)quinoline (L1), 8-(diphenylphosphino)quinoline (L2), 2-methyl-8-(diphenylphosphino)quinoline (L3), and 2-phenyl-8-(diphenylphosphino)quinoline (L4), were prepared and their molecular structures and spectroscopic properties were investigated. The single-crystal X-ray analysis and the P-31{H-1} NMR spectra of the products, [Pt(ppy)(Ln)](BF4 or OTf) {Cn; n = 1-4, ppy(-) = 2-(2'-pyridyl)phenyl, OTf- = trifluoromethanesulfonate} revealed the cis(P,C) configuration of the complex cations, although the square-planar Pt-II coordination geometry was considerably distorted. In particular, in the complexes C3 and C4 bearing sterically demanding 8-quinolylphosphines (L3 and L4), not only the tetrahedral distortion of the Pt-II coordination sphere but also a deviation of the Pt-II center from the planar chelate ring, i.e., an envelope-type distortion of the chelating quinolylphosphine coordination was observed. All complexes were stable in solution toward the addition of halide anions. However, a fluxional behavior of complexes C3 and C4, owing to the restricted inversion of the distorted coordination sphere, was observed in the temperature-dependent H-1 NMR spectra.
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