The Grubbs catalyst – dichlorido(1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene)-({5-nitro-2-[(propan-2-yl)oxy]phenyl}methylidene)ruthenium(II) – some observations on the crystallography and stereochemistry of a racemic mimic pair

Zeitschrift für Kristallographie - Crystalline Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 17, 2025

Abstract The title species has been studied in two crystalline forms resulting from reports describing (1) a centrosymmetric form [ P 2 1 / n , Z ′ = 1.0] and (2) Sohncke 2.0; Flack parameter −0.04(2)]. They are related by the fact that (a) have, approximately, same cell constants, while (b) is doubled latter course of losing n-glide plane. existence displaying such remarkable relationship was noted approximately 75 years ago, but, ignored probably because discoverers (see below) never completed necessary experimental work to fully document phenomenon, inasmuch as crystallography its infancy then synthesizing necessary, pure, chiral growing high-quality crystals major challenge which has, not even yet, accomplished. Moreover, O. Hassel, player this field, distracted his on chair-boat equilibrium cyclohexane rings systems for he eventually won Nobel Prize (1969). Herein, we have attempted contribute chapter curious crystallographic made more fascinating observation ruthenium Grubbs catalyst belongs racemic mimic class.

Language: Английский

Synthesis and Reactivity of an Olefin Metathesis-Catalyzing Ruthenium Complex with a Selenoether Moiety in the Benzylidene Ligand

ACS Omega, Journal Year: 2024, Volume and Issue: 9(52), P. 51604 - 51610

Published: Dec. 17, 2024

A Hoveyda–Grubbs (HG)-type olefin metathesis complex with a selenoether moiety at the terminus of phenoxy was synthesized. The showed direct selenium-atom coordination to ruthenium center, resulting in higher thermodynamic stability compared parent HG catalyst. selenium atom binding enhanced tolerance protic solvent molecules ring-closing N-tosyldiallylamide and diethyl diallylmalonate, also cross between 3-butenylbenzoate methyl acrylate. large activation enthalpy observed reaction n-butyl vinyl ether indicated an increased contribution "dissociative mechanism" during initiation catalytic cycle. Introducing coordinative atoms or functional groups terminal is useful strategy regulate thermostability HG-type catalysts.

Language: Английский