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Synthesis and Coordination Chemistry of New Asymmetric Donor/Acceptor Pincer Ligands, 1,3-C6H4(CH2PtBu(Rf))2 (Rf = CF3, C2F5)

Abstract

Syntheses of new asymmetric pincer precursors 1,3-C6H4{CH2P(tBu,X)}2 (tBu,XPCPH; X = Cl, SiMe3, OPh) and a new class of hybrid donor/acceptor pincer ligands 1,3-C6H4{CH2P(tBu,Rf)}2 (tBu,RfPCPH; Rf = CF3, C2F5) are reported. All tBu,XPCPH compounds are obtained as mixtures of meso and rac diastereomers in varying ratios (meso:rac ~ 4:1 to 3:2) which were used without separation. Treatment of Ru(cot)(cod) with tBu,CF3PCPH under 1 atm H2 in acetone at 20 C produced the hydride solvate (tBu,CF3PCP)Ru(acetone)xH which was not isolated, but could be trapped as stable diene complexes (tBu,CF3PCP)Ru(L)2H (L2 = cod (1), nbd (2)). Catalytic cyclooctane dehydrogenation studies demonstrate that 2 has ~50% the activity of (CF3PCP)Ru(cod)(H), but significantly higher catalyst stability and is able to operate at higher catalyst loading concentrations without deactivation via bimolecular decomposition.

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Publication details

The article was received on 04 Jul 2018, accepted on 02 Aug 2018 and first published on 09 Aug 2018


Article type: Paper
DOI: 10.1039/C8DT02738B
Citation: Dalton Trans., 2018, Accepted Manuscript
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    Synthesis and Coordination Chemistry of New Asymmetric Donor/Acceptor Pincer Ligands, 1,3-C6H4(CH2PtBu(Rf))2 (Rf = CF3, C2F5)

    S. DEBNATH, G. Venegas, N. Arulsamy and D. M. Roddick, Dalton Trans., 2018, Accepted Manuscript , DOI: 10.1039/C8DT02738B

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