Methylation of a nitrosylruthenium complex bearing a hydridotris(pyrazolyl)borate ligand

Arikawa, Yasuhiro; Yamaguchi, Soseki; Haige, Ryohei; Oshiro, Eriko; Umakoshi, Keisuke; Onishi, Masayoshi

doi:10.1016/j.jorganchem.2013.12.054

Cited by 4 publications

(2 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We attempted to synthesize a precursor to [TpRu(NO)(Ph)] + by first preparing TpRu(NO)(OTf)Ph (OTf = trifluoromethanesulfonate) as shown in Scheme 2 TpRu(NO)Cl2 (1) was synthesized following a reported procedure with slight modifica tion (see Experimental Section). [49,50] The dichloride complex 1 was characterized by IR and 1 H NMR spectroscopy. The IR spectrum of 1 exhibited an intense absorption at 1898 cm -1 , which is due to NO stretching, and in the 1 H NMR spectrum of 1, resonances corre sponding to the three Tp-pyrazolyl groups in 1 appear as two sets of signals with a 1:2 integration ratio, which is consistent with the expected mirror plane of symmetry (Figure S1).…”

Section: Attempted Synthesis Of Complexes That Provide Access To [Tpr...mentioning

confidence: 99%

See 1 more Smart Citation

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

et al. 2022

View full text Add to dashboard Cite

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.

show abstract

Section: Attempted Synthesis Of Complexes That Provide Access To [Tpr...mentioning

confidence: 99%

“…We attempted to synthesize a precursor to [TpRu(NO)(Ph)] + by first preparing TpRu (NO)(OTf)Ph (OTf = trifluoromethanesulfonate) as shown in Scheme 2. TpRu(NO)Cl 2 (1) was synthesized following a reported procedure with slight modification (see Section 4) [49,50]. The dichloride complex 1 was characterized by IR and 1 H NMR spectroscopy.…”

Section: Introductionmentioning

confidence: 99%