Dalton Transactions p. 12420 - 12430 (2018)
Update date:2022-08-11
Topics:
Debnath, Suman
Venegas, Gabriel
Arulsamy, Navamoney
Roddick, Dean M.
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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