Ligand effects on the Pt(II) → Pt(0) reduction of dichlorobis(tertiary phosphine)platinum(II) complexes: Correlations between electrochemical data,spectroscopic data,and electronic ligand parameters |
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| Authors: | J.A. Davies V. Uma J.G. Mierzwiak |
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| Affiliation: | Department of Chemistry, College of Arts and Sciences, University of Toledo, Toledo, OH 43606 U.S.A. |
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| Abstract: | Cyclic voltammetry has been employed to study the diffusive, irreversible platinum(II) → platinum(0) reduction of three sets of structurally related complexes: cis-[PtCl2P{p-C6H4X}3)2] (X = H, CH3, Cl, F, OCH3, N(CH3)2); cis-[PtCl2(PPh2R)2] (R = CH3, n-C3H7, n-C5H11, n-C6H13, n-C12H25) and cis-[PtCl2(PR3)2] (R = CH3, C2H5, CH2ch2CN). Relationships between the peak potentials for the Pt(II) → Pt(0) reduction and thermodynamic parameters which measure the electronic properties of the ligands are shown to exist for complexes of P{p-C6H4X}3 ligands, implying a thermodynamic origin for the sensitivity of the peak potentials to structural change. Complexes of both P{p-C6H4X}3 and PPh2R ligands show correlations between peak potentials for reduction and the 31P{1H} NMR spectroscopic parameter, 1J(195Pt, 31P). Correlations with values of δ(31P) exist in both cases, but a correlation with the coordination chemical shift, Δδ(31P), exists for complexes of PPh2R, and not for complexes of P{C6H4X}3. Complexes of PR3 ligands show no correlation between the peak potentials measured for the Pt(II) → Pt(0) reduction and electronic or spectroscopic parameters, except possibly 1J(195Pt, 31P). |
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| Keywords: | To whom correspondence should be addressed. |
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