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Steric distortion of planar NiP2N2 chromophores: a spectral, cyclic voltammetric and single crystal X-ray structural study

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Abstract

The complexes trans-[Ni(4-MP)2(NCS)2]·MeCN (1) and trans-[Ni(3-MP)2(NCS)2] (2) (4-MP = tri(4-methylphenyl)phosphine, 3-MP = tri(3-methylphenyl)phosphine) were prepared and characterized by IR, UV–visible, NMR spectra, CV, TGA and single crystal X-ray crystallography. Both the complexes have planar geometry and are diamagnetic. The Ni–P distances in both complexes are relatively short as a result of strong back donation from nickel to phosphorus. The phenyl rings in the 3-MP analogue (2) show increased pitching with reference to the plane formed by the ipso carbons due to increased steric effects. For complex (2), the N–Ni–N and P–Ni–P angles are significantly lower than the almost linear N–Ni–N and N–Ni–P angles observed for both complex (1) and trans-[Ni(PPh3)2(NCS)2]. This observation indicates that the 3-methylphosphine ligand forces complex (2) to distort towards a tetrahedral geometry. IR spectra of both complexes show strong bands around 2,090 cm−1 due to N-coordinated thiocyanate, while the electronic spectra contain d–d transitions around 452 nm. Cyclic voltammograms show that the irreversible one-electron reduction potentials increase in the following order: trans- [Ni(PPh3)2(NCS)2] < trans- [Ni(3-MP)2(NCS)2] < trans-[Ni(4-MP)2(NCS)2], revealing the electron releasing effect of the methyl groups. The planar complexes exhibit interallogony in coordinating solvents.

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Acknowledgments

One of the authors (RTK) thanks CSIR, New Delhi, India, for the financial support as a JRF (NET).

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Authors and Affiliations

  1. Department of Chemistry, Annamalai University, Annamalainagar, 608 002, India

    K. Ramalingam

  2. Department of Chemistry, Anna University of Technology, Tiruchirappalli, Tamilnadu, 620 024, India

    R. Thiruneelakandan

  3. Department of General and Inorganic Chemistry, University of Parma, 43100, Parma, Italy

    G. Bocelli & L. Righi

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  1. K. Ramalingam
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  2. R. Thiruneelakandan
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  3. G. Bocelli
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  4. L. Righi
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Correspondence to K. Ramalingam.

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Ramalingam, K., Thiruneelakandan, R., Bocelli, G. et al. Steric distortion of planar NiP2N2 chromophores: a spectral, cyclic voltammetric and single crystal X-ray structural study. Transition Met Chem 37, 265–270 (2012). https://doi.org/10.1007/s11243-012-9584-5

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