Dual Ethylene and CS2 Insertion at an Amidoquinoline Nickel(II) Alkyl Complex Enables CS2-End-Capped Oligoethylene
- 1Institute for Sustainable and Circular Chemistry, Organic Chemistry & Catalysis, Utrecht University, Universiteitsweg 99, Utrecht, Netherlands, 3584 CG
- 2Industrial Sustainable Chemistry, University of Amsterdam, Science Park 904, Amsterdam, Netherlands, 1098 XH
- 3Faculty of Science, Utrecht University, Universiteitsweg 99, Utrecht, Netherlands
Abstract
Combining olefin and heteroallene (e.g., CO 2 and CS 2 ) migratory insertion during chain-growth polymerization could provide a powerful route to polyolefin-like materials bearing chemically addressable functionalities and defined degradation sites. Herein, we report a neutral Ni(II)-methyl complex 1 supported by an amidoquinoline ligand that exhibits dual reactivity, mediating both ethylene oligomerization at 1 bar and 70 °C and, separately, CS 2 insertion at the Ni–CH3 bond at ambient temperature to afford the corresponding κ 2 (S,S)-dithioacetate complex 2. DFT calculations rationalize the rapid CS 2 insertion mechanism, proceeding through an η 2 –CS 2 pentacoordinate transition state with an overall barrier of 15.3 kcal mol–1. Remarkably, sequential ethylene oligomerization followed by CS 2 addition provides spectroscopic evidence for dithioacetate end-capped oligoethylene, demonstrating that the Ni–C bonds generated during ethylene chain growth polymerization remain competent for heteroallene insertion. Together, these results provide an important step forward toward the synthesis of chemically addressable polyolefin-like materials directly from small-molecules building blocks.
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BibTeX
@misc{grabbet2026dual,
title = {{Dual Ethylene and CS2 Insertion at an Amidoquinoline Nickel(II) Alkyl Complex Enables CS2-End-Capped Oligoethylene}},
author = {Björn Grabbet and Jade Wimmers and Martin Lutz and Arnaud Thevenon},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008375/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008375/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Dual Ethylene and CS2 Insertion at an Amidoquinoline Nickel(II) Alkyl Complex Enables CS2-End-Capped Oligoethylene
AU - Björn Grabbet
AU - Jade Wimmers
AU - Martin Lutz
AU - Arnaud Thevenon
PY - 2026
DA - 2026/09/06
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008375/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008375/v1
AB - Combining olefin and heteroallene (e.g., CO 2 and CS 2 ) migratory insertion during chain-growth polymerization could provide a powerful route to polyolefin-like materials bearing chemically addressable functionalities and defined degradation sites. Herein, we report a neutral Ni(II)-methyl complex 1 supported by an amidoquinoline ligand that exhibits dual reactivity, mediating both ethylene oligomerization at 1 bar and 70 °C and, separately, CS 2 insertion at the Ni–CH3 bond at ambient temperature to afford the corresponding κ 2 (S,S)-dithioacetate complex 2. DFT calculations rationalize the rapid CS 2 insertion mechanism, proceeding through an η 2 –CS 2 pentacoordinate transition state with an overall barrier of 15.3 kcal mol–1. Remarkably, sequential ethylene oligomerization followed by CS 2 addition provides spectroscopic evidence for dithioacetate end-capped oligoethylene, demonstrating that the Ni–C bonds generated during ethylene chain growth polymerization remain competent for heteroallene insertion. Together, these results provide an important step forward toward the synthesis of chemically addressable polyolefin-like materials directly from small-molecules building blocks.
ER -