Competitive Ligand Exchange and Dissociation in Ru Indenyl Complexes

Belli, Roman G.; Wu, Yang; Ji, Hyewon; Joshi, Anuj; Yunker, Lars P. E.; McIndoe, J. Scott; Rosenberg, Lisa

doi:10.1021/acs.inorgchem.8b02915

Cited by 26 publications

(30 citation statements)

References 46 publications

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“…The consequences of these differences can be rigorously examined through numerical simulation of the various competing processes using the COPASI software, [35,36] subject to certain simplifying assumptions. The first of these is that any process involving monomeric Me 2 AlX (X = Me or OH) forming a dimeric species or a tetrahedral intermediate (e. g. Me 3 Al-OH 2 ) is essentially diffusion controlled, but possibly reversible, while methane elimination from various species is chemically controlled but irreversible.…”

Section: Initial Hydrolysis Stepsmentioning

confidence: 99%

Formation and Structure of Hydrolytic Methylaluminoxane Activators

Collins

Joshi²,

Linnolahti

2021

Chemistry A European J

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Methylaluminoxane (MAO) activators have sheet structures which form ion-pairs on reaction of neutral donors such as octamethyltrisiloxane (OMTS). The ion-pairs can be detected by electrospray ionization mass spectrometry (ESI-MS) in polar media. The growth of these reactive precursors during hydrolysis of Me 3 Al can be monitored using ESI-MS. Density functional theory, combined with numerical simulation of growth, indicates that this process involves rapid formation of low MW oligomers, followed by assembly of these species into low MW sheets. These can grow through further addition of low MW oligomers or by fusion into larger sheets. The mechanism of these growth processes leads to the prediction that even-numbered sheets should be favored, and this surprising result is confirmed by ESI-MS monitoring experiments of both activator growth and MAO aging.

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Section: Initial Hydrolysis Stepsmentioning

confidence: 99%

Formation and Structure of Hydrolytic Methylaluminoxane Activators

Collins

Joshi²,

Linnolahti

2021

Chemistry A European J

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“…On the other hand, dissociation of an X‐type ligand from a positively charged ion would require charge separation and solvent stabilization and will therefore not occur during MS/MS (in the negative ion mode dissociation of an X‐type ligand is possible (eg, [PtCl 4 ] 2− → [PtCl 3 ] − + Cl − ). The absence of solvent interactions also makes C‐H activation processes such as orthometallation common in the gas phase and makes dissociation of chelating ligands highly unlikely. In general, processes involving highly polarized transition states will be disfavored.…”

Section: The Fundamentals Of Assigning Esi‐ms Spectramentioning

confidence: 99%

Assigning the ESI mass spectra of organometallic and coordination compounds

McIndoe

Vikse

2019

J Mass Spectrom

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Electrospray ionization mass spectrometry (ESI‐MS) is a useful technique for solving organometallic and coordination chemistry characterization problems that are difficult to address using traditional methods. However, assigning the ESI mass spectra of such compounds can be challenging, and the considerations involved in doing so are quite different from assigning the mass spectra of purely organic samples. This is a tutorial article for organometallic/coordination chemists using ESI‐MS to analyze pure compounds or reaction mixtures. The fundamentals of assigning ESI mass spectra are discussed within the context of organometallic and coordination systems. The types of ions commonly observed by ESI‐MS are categorized and described. Finally, a step‐by‐step guide for the assignment of organometallic and coordination chemistry ESI mass spectra is provided along with two case studies.

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“…PSI‐ESI‐MS has also proven useful for Belli et al. in comparing the affinity of select secondary and tertiary phosphines for cationic ruthenium centers [81] . Competitive substitution reactions were analyzed in real time to assess the relative binding strength and measure the relative kinetics.…”

Section: Applicationsmentioning

confidence: 99%

“…PSI-ESI-MS has also proven useful for Belli et al in comparing the affinity of select secondary and tertiary phosphines for cationic ruthenium centers. [81] Competitive substitution reactions were analyzed in real time to assess the relative binding strength and measure the relative kinetics. A dissociative mechanism for substitution of NCPh with secondary phosphines on [Ru(η 5 -indenyl)(NCPh)(PPh 3 ) 2 ] + was revealed, as well as reaction kinetics.…”

Section: Applications In Catalysismentioning

confidence: 99%

Pressurized Sample Infusion

et al. 2021

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Pressurized sample infusion (PSI) is a simple and effective means of continuously introducing a solution to an electrospray ionization mass spectrometry (ESI‐MS) source. It allows for acquisition of real‐time data in an air‐ and moisture‐free environment and requires minimal additional infrastructure. It is applicable for use for any reaction in which one or more components are detectable by ESI‐MS and for which time‐course information is desired over a time scale of seconds to minutes. The strengths and weaknesses of the method are critically examined, and technique tips and tricks are provided to enable maximal effectiveness when employing this approach to continuous monitoring of complex reaction mixtures.

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Competitive Ligand Exchange and Dissociation in Ru Indenyl Complexes

Abstract: Kinetic profiles obtained from monitoring the solution phase substitution chemistry of [Ru(η 5 -indenyl)(NCPh)(PPh 3 ) 2 ] + (1) by both ESI-MS and 31 P{ 1 H} NMR are essentially identical, despite an

Cited by 26 publications

References 46 publications

Formation and Structure of Hydrolytic Methylaluminoxane Activators

Formation and Structure of Hydrolytic Methylaluminoxane Activators

Assigning the ESI mass spectra of organometallic and coordination compounds

Pressurized Sample Infusion

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