Electron-Deficient Ru(II) Complexes as Catalyst Precursors for Ethylene Hydrophenylation

Abstract

Ruthenium(II) complexes with the general formula TpRu(L)(NCMe)Ph (Tp = hydrido(trispyrazolyl)borate, L = CO, PMe3, P(OCH2)3CEt, P(pyr)3, P(OCH2)2(O)CCH3) have previously been shown to catalyze arene alkylation via Ru-mediated arene C–H activation including the conversion of benzene and ethylene to ethylbenzene. Previous studies have suggested that the catalytic performance of these TpRu(II) catalysts increases with reduced electron-density at the Ru center. Herein, three new structurally related Ru(II) complexes are synthesized, characterized, and studied for possible catalytic benzene ethylation. TpRu(NO)Ph2 exhibited low stability due to the facile elimination of biphenyl. The Ru(II) complex (TpBr3)Ru(NCMe)(P(OCH2)3CEt)Ph (TpBr3 = hydridotris(3,4,5-tribromopyrazol-1-yl)borate) showed no catalytic activity for the conversion of benzene and ethylene to ethylbenzene, likely due to the steric bulk introduced by the bromine substituents. (Ttz)Ru(NCMe)(P(OCH2)3CEt)Ph (Ttz = hydridotris(1,2,4-triazol-1-yl)borate) catalyzed approximately 150 turnover numbers (TONs) of ethylbenzene at 120 °C in the presence of Lewis acid additives. Here, we compare the activity and features of catalysis using (Ttz)Ru(NCMe)(P(OCH2)3CEt)Ph to previously reported catalysis based on TpRu(L)(NCMe)Ph catalyst precursors.

Keywords

• olefin hydroarylation
• ruthenium
• catalysis
• ethylbenzene
• C–H activation