Three-Coordinate Zinc Methyl Complexes with Sterically Demanding Formazanate Ligands

Folkert de Vries; Raquel Travieso-Puente; Peter Roewen; Edwin Otten

doi:10.1021/acs.organomet.0c00720

Three-Coordinate Zinc Methyl Complexes with Sterically Demanding Formazanate Ligands

Folkert de Vries, Raquel Travieso-Puente, Peter Roewen, Edwin Otten^*

^*Corresponding author for this work

Molecular Inorganic Chemistry

Research output: Contribution to journal › Article › Academic › peer-review

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Abstract

A series of heteroleptic three-coordinate mono(formazanate)zinc methyl complexes were synthesized, and the influence of the ligand on the structure as well as redox and optical properties of these complexes was investigated. The heteroleptic mono(formazanate)zinc methyl complexes were found to show ligand redistribution in solution, reminiscent of the Schlenk equilibrium, to generate an equilibrium mixture containing the corresponding homoleptic complexes as well. Monitoring the approach to equilibrium by NMR spectroscopy in benzene-d(6) allowed determination of the forward and backward rate constants. A correlation was found between the steric environment around the zinc center and equilibrium concentration of (formazanate)zinc methyl compounds, whereas the kinetics for approach to equilibrium are also dependent on the electronic properties.

Original language	English
Pages (from-to)	63-71
Number of pages	9
Journal	Organometallics
Volume	40
Issue number	1
DOIs	https://doi.org/10.1021/acs.organomet.0c00720
Publication status	Published - 11-Jan-2021

Keywords

RING-OPENING POLYMERIZATION
ALTERNATING COPOLYMERIZATION
MAGNESIUM
CATALYSTS
DERIVATIVES
CHEMISTRY
EPOXIDES
ANALOGS
LACTIDE
CO2

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10.1021/acs.organomet.0c00720Licence: CC BY-NC-ND

Three-Coordinate Zinc Methyl Complexes with Sterically Demanding Formazanate LigandsFinal publisher's version, 2.44 MBLicence: CC BY-NC-ND

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CCDC 2033367: Experimental Crystal Structure Determination
de Vries, F. (Contributor), Travieso Puente, R. (Contributor), Roewen, P. (Contributor) & Otten, E. (Contributor), University of Groningen, 22-Sept-2020
DOI: 10.5517/ccdc.csd.cc267whv
Dataset
CCDC 2033368: Experimental Crystal Structure Determination
de Vries, F. (Contributor), Travieso Puente, R. (Contributor), Roewen, P. (Contributor) & Otten, E. (Contributor), University of Groningen, 22-Sept-2020
DOI: 10.5517/ccdc.csd.cc267wjw
Dataset
CCDC 2033361: Experimental Crystal Structure Determination
de Vries, F. (Contributor), Travieso Puente, R. (Contributor), Roewen, P. (Contributor) & Otten, E. (Contributor), University of Groningen, 22-Sept-2020
DOI: 10.5517/ccdc.csd.cc267w9n
Dataset

Cite this

@article{0b58e3e1c86f4cedb855a5d36e003c95,

title = "Three-Coordinate Zinc Methyl Complexes with Sterically Demanding Formazanate Ligands",

abstract = "A series of heteroleptic three-coordinate mono(formazanate)zinc methyl complexes were synthesized, and the influence of the ligand on the structure as well as redox and optical properties of these complexes was investigated. The heteroleptic mono(formazanate)zinc methyl complexes were found to show ligand redistribution in solution, reminiscent of the Schlenk equilibrium, to generate an equilibrium mixture containing the corresponding homoleptic complexes as well. Monitoring the approach to equilibrium by NMR spectroscopy in benzene-d(6) allowed determination of the forward and backward rate constants. A correlation was found between the steric environment around the zinc center and equilibrium concentration of (formazanate)zinc methyl compounds, whereas the kinetics for approach to equilibrium are also dependent on the electronic properties.",

keywords = "RING-OPENING POLYMERIZATION, ALTERNATING COPOLYMERIZATION, MAGNESIUM, CATALYSTS, DERIVATIVES, CHEMISTRY, EPOXIDES, ANALOGS, LACTIDE, CO2",

author = "{de Vries}, Folkert and Raquel Travieso-Puente and Peter Roewen and Edwin Otten",

year = "2021",

month = jan,

day = "11",

doi = "10.1021/acs.organomet.0c00720",

language = "English",

volume = "40",

pages = "63--71",

journal = "Organometallics",

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TY - JOUR

T1 - Three-Coordinate Zinc Methyl Complexes with Sterically Demanding Formazanate Ligands

AU - de Vries, Folkert

AU - Travieso-Puente, Raquel

AU - Roewen, Peter

AU - Otten, Edwin

PY - 2021/1/11

Y1 - 2021/1/11

N2 - A series of heteroleptic three-coordinate mono(formazanate)zinc methyl complexes were synthesized, and the influence of the ligand on the structure as well as redox and optical properties of these complexes was investigated. The heteroleptic mono(formazanate)zinc methyl complexes were found to show ligand redistribution in solution, reminiscent of the Schlenk equilibrium, to generate an equilibrium mixture containing the corresponding homoleptic complexes as well. Monitoring the approach to equilibrium by NMR spectroscopy in benzene-d(6) allowed determination of the forward and backward rate constants. A correlation was found between the steric environment around the zinc center and equilibrium concentration of (formazanate)zinc methyl compounds, whereas the kinetics for approach to equilibrium are also dependent on the electronic properties.

AB - A series of heteroleptic three-coordinate mono(formazanate)zinc methyl complexes were synthesized, and the influence of the ligand on the structure as well as redox and optical properties of these complexes was investigated. The heteroleptic mono(formazanate)zinc methyl complexes were found to show ligand redistribution in solution, reminiscent of the Schlenk equilibrium, to generate an equilibrium mixture containing the corresponding homoleptic complexes as well. Monitoring the approach to equilibrium by NMR spectroscopy in benzene-d(6) allowed determination of the forward and backward rate constants. A correlation was found between the steric environment around the zinc center and equilibrium concentration of (formazanate)zinc methyl compounds, whereas the kinetics for approach to equilibrium are also dependent on the electronic properties.

KW - RING-OPENING POLYMERIZATION

KW - ALTERNATING COPOLYMERIZATION

KW - MAGNESIUM

KW - CATALYSTS

KW - DERIVATIVES

KW - CHEMISTRY

KW - EPOXIDES

KW - ANALOGS

KW - LACTIDE

KW - CO2

U2 - 10.1021/acs.organomet.0c00720

DO - 10.1021/acs.organomet.0c00720

M3 - Article

SN - 0276-7333

VL - 40

SP - 63

EP - 71

JO - Organometallics

JF - Organometallics

IS - 1

ER -

Three-Coordinate Zinc Methyl Complexes with Sterically Demanding Formazanate Ligands

Abstract

Keywords

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Datasets

CCDC 2033367: Experimental Crystal Structure Determination

CCDC 2033368: Experimental Crystal Structure Determination

CCDC 2033361: Experimental Crystal Structure Determination

Cite this