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New insights into the biphasic "CO-free" Pauson-Khand cyclisation reaction through combined spectroscopy and multiple linear regression modelling
"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 applying in situ Raman spec...
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Published in: | Catalysis science & technology 2021-03, Vol.11 (4), p.1626-1636 |
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Main Authors: | , , , , , |
Format: | Article |
Language: | |
Online Access: | Get full text |
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Summary: | "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 applying
in situ
Raman 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, coupling
in situ
Raman 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.
Multiple linear regression modelling is used to analyse
in situ
Raman spectra recorded during a "CO-free" Pauson-Khand type cyclisation which enables a knowledge-driven optimisation protocol. |
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ISSN: | 2044-4753 2044-4761 |
DOI: | 10.1039/d0cy02267e |