Interaction of hydroperoxopalladium complexes, (TpR)(py)Pd–OOH, with hydroxo-nickel and -cobalt complexes, [(μ-OH)(MTpR′)]2(M = Ni, Co), leading to oxidative dehydrogenation of the saturated hydrocarbyl moiety in the ancillary ligand (TpiPr2)

Masato Kujime; Shiro Hikichi; Munetaka Akita

doi:10.1039/B307262M

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Interaction of hydroperoxopalladium complexes, (Tp^R)(py)Pd–OOH, with hydroxo-nickel and -cobalt complexes, [(μ-OH)(MTp^R′)]₂ (M = Ni, Co), leading to oxidative dehydrogenation of the saturated hydrocarbyl moiety in the ancillary ligand (Tp^iPr2)†

Masato Kujime,^a Shiro Hikichi ‡^a and Munetaka Akita*^a

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* Corresponding authors

^a Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
E-mail: makita@res.titech.ac.jp

Abstract

Treatment of hydroperoxopalladium complexes, (Tp^R)(py)Pd–OOH, with hydroxonickel complexes, [(μ-OH)NiTp^R′]₂, when either Tp^R or Tp^R′ is Tp^iPr2, results in dehydrogenation of an isopropyl group of the Tp^iPr2 ligand to give heterobimetallic di-μ-hydroxo complexes bearing the 3-isopropenyl-substituted Tp ligand [HB(pz^iPr2)₂(pz^{3-isopropenyl-5-iPr}). Similar dehydrogenation is observed for the reaction with the hydroxocobalt complex bearing the Tp^iPr2 ligand. The dehydrogenated products are characterized by spectroscopic and crystallographic methods and a mechanism involving a heterobimetallic μ-peroxo intermediate formed via dehydrative condensation has been proposed for the oxidative dehydrogenation.

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Article information

DOI: https://doi.org/10.1039/B307262M
Article type: Paper
Submitted: 25 Jun 2003
Accepted: 29 Jul 2003
First published: 13 Aug 2003

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Dalton Trans., 2003, 3506-3515

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Interaction of hydroperoxopalladium complexes, (Tp^R)(py)Pd–OOH, with hydroxo-nickel and -cobalt complexes, [(μ-OH)(MTp^R′)]₂ (M = Ni, Co), leading to oxidative dehydrogenation of the saturated hydrocarbyl moiety in the ancillary ligand (Tp^iPr2)

M. Kujime, S. Hikichi and M. Akita, Dalton Trans., 2003, 3506 DOI: 10.1039/B307262M

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Dalton Transactions