Issue 35, 2018

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 with combining low line]), nbd ([2 with combining low line])). Catalytic cyclooctane dehydrogenation studies demonstrate that [2 with combining low line] 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.

Graphical abstract: Synthesis and coordination chemistry of new asymmetric donor/acceptor pincer ligands, 1,3-C6H4(CH2PtBu(Rf))2 (Rf = CF3, C2F5)

Supplementary files

Article information

Article type
Paper
Submitted
04 Qad 2018
Accepted
02 Leq 2018
First published
09 Leq 2018

Dalton Trans., 2018,47, 12420-12430

Author version available

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, 47, 12420 DOI: 10.1039/C8DT02738B

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