Formation and coordination modes of the C4E4 moiety (E = COOMe) bound to two palladium(II) moieties

Tetsuro Murahashi; Taketoshi Okuno; Kentaro Usui; Kohei Takase; Toshiaki Otani; Sensuke Ogoshi; Hideo Kurosawa

doi:10.1039/C0DT01169J

Formation and coordination modes of the C₄E₄ moiety (E = COOMe) bound to two palladium(ii) moieties†

Tetsuro Murahashi,*^a Taketoshi Okuno,^a Kentaro Usui,^a Kohei Takase,^a Toshiaki Otani,^a Sensuke Ogoshi^a and Hideo Kurosawa*^a

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* Corresponding authors

^a Department of Applied Chemistry, Graduate School of Engineering, Osaka University, and PRESTO, Japan Science and Technology Agency, Suita, Osaka, Japan
E-mail: tetsu@chem.eng.osaka-u.ac.jp
Fax: (+81)6 6879 7394

Abstract

The transmetallation of the palladacyclopentadiene complex Pd{C(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy) with the dicationic Pd^II complex [Pd(bipy)(CH₃CN)₂][BF₄]₂ afforded a terminally σ-palladated diene complex [Pd₂{μ-η¹:η¹-C(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy)₂(CH₃CN)₂][BF₄]₂. It was revealed by X-ray crystallographic analysis that replacement of the acetonitrile ligands in a terminally σ-palladated diene complex with PPh₃ ligands resulted in the conformation change of the σ-palladated diene moiety from skewed s-cis to planar s-trans. Treatment of a bis-triphenylphosphine dipalladium complex [Pd₂(PPh₃)₂(CH₃CN)₄][PF₆]₂ with dimethoxyacetylene dicarboxylate (DMAD) (1 equiv.) in acetonitrile resulted in the insertion of DMAD to the Pd–Pd bond to afford [Pd₂{μ-η¹:η¹-C(COOMe)C(COOMe)}(PPh₃)₂(CH₃CN)₄][PF₆]₂. Addition of the second DMAD gave the ylide-type complex [Pd₂{μ-η²:η³-C(COOMe)C(COOMe)C(COOMe)C(COOMe)(PPh₃)}(PPh₃)₂(CH₃CN)₃][PF₆]₂ of which the structure was determined by X-ray crystallographic analysis.

This article is part of the themed collection: New Talent: Asia

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Article information

DOI: https://doi.org/10.1039/C0DT01169J
Article type: Paper
Submitted: 04 Sep 2010
Accepted: 06 Jan 2011
First published: 03 Feb 2011

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Dalton Trans., 2011,40, 2383-2387

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Formation and coordination modes of the C₄E₄ moiety (E = COOMe) bound to two palladium(II) moieties

T. Murahashi, T. Okuno, K. Usui, K. Takase, T. Otani, S. Ogoshi and H. Kurosawa, Dalton Trans., 2011, 40, 2383 DOI: 10.1039/C0DT01169J

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