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Neutral and cationic (pyrazolylmethyl)pyridine palladium(II) complexes: kinetics and chemoselectivity studies in hydrogenation of alkenes and alkynes

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Abstract

Reactions of (3,5-dimethylpyrazolylmethyl)pyridine (L1) and (3,5-diphenylpyrazolylmethyl)pyridine (L2) with either [PdCl2(NCMe)2] or [PdClMe(COD)] afforded the respective neutral palladium complexes, [PdCl2(L1)] (1), [PdCl2(L2)] (2) and [PdClMe(L1)] (3). Treatment of complex 1 with equimolar amounts of PPh3 or PPh3/NaBAr4 produced the corresponding cationic complexes [Pd(L1)ClPPh3]Cl (4) and [Pd(L1)ClPPh3]BAr4 (5), respectively. Complexes 1–5 formed active catalysts in hydrogenation of alkenes and alkynes. Isomerization reactions were predominant in the hydrogenation reactions of terminal alkenes, while hydrogenation of alkynes involved a two-step process via alkene intermediates prior to the formation of the respective alkenes. The lack of induction periods in the hydrogenation reactions in addition to pseudo-first-order kinetics with respect to the substrates established the homogeneous nature of the active species.

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Acknowledgments

The authors are grateful for the financial support received from the University of KwaZulu-Natal.

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Authors and Affiliations

  1. School of Chemistry and Physics, University of KwaZulu-Natal, Private Bag X01, Scottsville, Pietermaritzburg, 3209, South Africa

    Stephen O. Ojwach & Aloice O. Ogweno

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  1. Stephen O. Ojwach
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  2. Aloice O. Ogweno
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Correspondence to Stephen O. Ojwach.

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Ojwach, S.O., Ogweno, A.O. Neutral and cationic (pyrazolylmethyl)pyridine palladium(II) complexes: kinetics and chemoselectivity studies in hydrogenation of alkenes and alkynes. Transit Met Chem 41, 539–546 (2016). https://doi.org/10.1007/s11243-016-0050-7

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