New insights into the biphasic “CO-free” Pauson-Khand cyclisation reaction through combinedin situspectroscopy and multiple linear regression modelling

Geitner R, Huang T, Kupfer S, Gräfe S, Meirer F, Weckhuysen BM (2021)

Publication Type: Journal article

Publication year: 2021

Journal

Catalysis: Science and Technology Royal Society of Chemistry

Book Volume: 11

Pages Range: 1626-1636

Journal Issue: 4

DOI: 10.1039/d0cy02267e

Abstract

“CO-free” carbonylations are catalytic reactions, which strive to replace toxic synthesis gas with less harmful surrogate molecules like formaldehyde. This study sheds light on the mechanism of the biphasic, Rh-catalysed Pauson-Khand type cyclisation reaction by applyingin situRaman spectroscopy together with NMR, dynamic light scattering measurements, and quantum chemical calculations. The reaction is particularly challenging to analyse as the Rh-catalyst features different ligands in the aqueous and organic phase. To tackle this challenge, a novel approach was designed, couplingin situRaman spectroscopy with an advanced data analysis model in the form of multiple linear regression. This fruitful combination of highly specific vibrational spectroscopy with state-of-the-art data analysis allowed not only identification of a new reaction mechanism, but also identification of parameters to accelerate the “CO-free” Pauson-Khand cyclisation,i.e.using mononuclear Rh-phosphine complexes with labile ligands, small organic micelles formed by an increased surfactant concentration, low formaldehyde concentration, and elevated temperature. This novel knowledge-driven optimisation protocol is superior to simple qualitative optimization routines and can be transferred to other reactions and spectroscopy techniques.

Involved external institutions

Universiteit Utrecht (UU) / Utrecht University NL Netherlands (NL) Friedrich-Schiller-Universität Jena DE Germany (DE)

How to cite

APA:

Geitner, R., Huang, T., Kupfer, S., Gräfe, S., Meirer, F., & Weckhuysen, B.M. (2021). New insights into the biphasic “CO-free” Pauson-Khand cyclisation reaction through combinedin situspectroscopy and multiple linear regression modelling. Catalysis: Science and Technology, 11(4), 1626-1636. https://dx.doi.org/10.1039/d0cy02267e

MLA:

Geitner, Robert, et al. "New insights into the biphasic “CO-free” Pauson-Khand cyclisation reaction through combinedin situspectroscopy and multiple linear regression modelling." Catalysis: Science and Technology 11.4 (2021): 1626-1636.

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