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Issue 35, 2011
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Original palladium pincer complexes deriving from 1,3-bis(thiophosphinoyl)indene proligands: Csp3–H versus Csp2–H bond activation

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Abstract

A series of original 2-indenylidene palladium pincer complexes {PdL[Ind(Ph2P[double bond, length as m-dash]S)2]} (L = HNCy2, PPh3, Cl) have been prepared by double C–H activation of a 1,3-bis(thiophosphinoyl)indene proligand. Crystallographic analyses and DFT calculations indicate that the bonding situation of the {Pd[Ind(Ph2P[double bond, length as m-dash]S)2]} fragment is essentially governed by the conjugated and rigid nature of the dianionic pincer ligand, the nature of the coligand having little influence. The formation of the 2-indenylidene complexes involves either a 2-indenyl pincer or a four-membered cyclometalated complex as an intermediate, suggesting that Csp2–H or Csp3–H bond activation takes place. However, deuterium labelling experiences show that in all cases, Csp3–H bond activation occurs followed eventually by a Pd/H exchange. Nevertheless, evidence for direct Csp2–H bond activation under mild conditions is obtained when a methyl group is introduced at the indene proligand to prevent Csp3–H bond activation. The ensuing dissymmetrical 2-indenyl palladium pincer complex has been fully characterized.

Graphical abstract: Original palladium pincer complexes deriving from 1,3-bis(thiophosphinoyl)indene proligands: Csp3–H versus Csp2–H bond activation

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Publication details

The article was received on 20 Jan 2011, accepted on 07 Mar 2011 and first published on 08 Apr 2011


Article type: Paper
DOI: 10.1039/C1DT10118H
Citation: Dalton Trans., 2011,40, 8912-8921
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    Original palladium pincer complexes deriving from 1,3-bis(thiophosphinoyl)indene proligands: Csp3–H versus Csp2–H bond activation

    N. Nebra, J. Lisena, N. Saffon, L. Maron, B. Martin-Vaca and D. Bourissou, Dalton Trans., 2011, 40, 8912
    DOI: 10.1039/C1DT10118H

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