The synthesis and single-crystal X-ray structures of palladium(II) and platinum(II) complexes of the difluorovinyl and 1-chloro-2-fluorovinyl-substituted phosphines, PPh2(Z-CFCFH) and PPh2(E-CClCFH) |
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Authors: | Nicholas A Barnes Cheryl Fish James V Morey Robin G Pritchard John E Warren |
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Institution: | School of Chemistry, The University of Manchester, Oxford Rd, Manchester, M13 9PL, UK |
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Abstract: | The coordination chemistry of the fluorovinyl substituted phosphines PPh2(Z-CF CFH) and PPh2(E-CCl CFH) with K2MX4 (M = Pd, Pt; X = Cl, Br, and I) salts has been investigated resulting in the first reported palladium(II) and platinum(II) complexes of phosphines containing partially fluorinated vinyl groups. The complexes have been characterised by a combination of multinuclear 1H, 13C{1H}, 19F, 31P{1H}] NMR spectroscopy, and IR/Raman spectroscopy. The single-crystal X-ray structures of trans-PdX2{PPh2(CF CFH)}2], X = Cl (1), Br (2), I (3), trans-PdCl2{PPh2(CCl CFH)}2] (4), cis-PtX2{PPh2(CF CFH)}2], X = Cl (5), Br (6), trans-PtI2{PPh2(CF CFH)}2] (7), and both cis- and trans-PtCl2{PPh2(CCl CFH)}2] (8), have been determined. Results obtained from spectroscopic and crystallographic data suggest that replacement of a β-fluorine by hydrogen, whilst reducing the steric demand of the ligand, has little effect on the electronic character of the ligand. The presence of a proton in the vinyl group results in short proton-halide secondary interactions in the solid state (d(H?X) = 2.72(3) for 1, and 2.92(5) Å for 2) forming an infinite chain ribbon motif. |
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Keywords: | Fluorovinyl Phosphine Coordination chemistry |
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