Pincer Nickel Metalloligands for the Stabilization of Alkali Metal Alkoxide Aggregates
- 1Tianjin Normal University , , 393 BinShui West Road , ,
- 2Université de Montréal , , Complexe Des Sciences, 1375 Avenue Thérèse-Lavoie-Roux, Montréal , ,
Abstract
The structural chemistry of alkali metal alkoxides remains challenging to elucidate because of their high reactivity and tendency to form ill-defined aggregates. Herein, we report two complementary pincer nickel platforms that serve as metalloligands to stabilize well-defined multinuclear aggregates of sodium and potassium alkoxides. The reaction of a POCOP–NiBr pincer complex with MeLi or NaOtBu led to unexpected double C–O bond cleavage of the pincer framework, generating anionic oxygen-rich fragments that assembled into a zwitterionic trinuclear lithium complex {(η3-allyl)Ni}2(μ,κP:κO-iPr2PO)4[Li3(Br)(κO-iPr2P(O)Me)] (1) and a hexanuclear sodium cluster {(η3-allyl)Ni}2(μ,κP:κO-iPr2PO)4[Na6(μ4-OtBu)2(μ-OtBu)2(μ-OtBuH)2] (2). In stark contrast, the unsymmetrical complex (κN,κC,κN′-NCN)NiBr (3) reacts with KOtBu to form a centrosymmetric trinickel species {(κN,κC,κN′-NCN:η4-Ar,η4-Ar)Ni(μ3-O)K2}2Ni(μ3-OtBu)4 (4) bridged by four KOtBu moieties, in which the NCN ligand framework remains intact. In 4, the central Ni adopts a distorted tetrahedral geometry coordinated by four oxygen atoms, while each potassium center completes its coordination sphere through three oxygen atoms and an η4-interaction with a pendant phenyl group, revealing a rare κK,κO bridging mode for KOtBu. Comprehensive single-crystal X-ray diffraction analyses confirm all structures. These results demonstrate the capacity of pincer nickel halides to stabilize otherwise elusive alkali metal alkoxide aggregates and provide new insights into the ligand-directed structural diversity of these important reagents.
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BibTeX
@article{liu2026pincer,
title = {{Pincer Nickel Metalloligands for the Stabilization of Alkali Metal Alkoxide Aggregates}},
author = {Yating Liu and Weichao Song and Daniel Chartrand and Pengchong Xue and Jingjun Hao and Davit Zargarian},
journal = {ACS Omega},
year = {2026},
month = oct,
doi = {10.1021/acsomega.6c08837},
url = {https://pubs.acs.org/acsodf/article/11/42/65886/5451593/Pincer-Nickel-Metalloligands-for-the-Stabilization},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - Pincer Nickel Metalloligands for the Stabilization of Alkali Metal Alkoxide Aggregates
AU - Yating Liu
AU - Weichao Song
AU - Daniel Chartrand
AU - Pengchong Xue
AU - Jingjun Hao
AU - Davit Zargarian
PY - 2026
DA - 2026/10/15
JO - ACS Omega
DO - 10.1021/acsomega.6c08837
UR - https://pubs.acs.org/acsodf/article/11/42/65886/5451593/Pincer-Nickel-Metalloligands-for-the-Stabilization
AB - The structural chemistry of alkali metal alkoxides remains challenging to elucidate because of their high reactivity and tendency to form ill-defined aggregates. Herein, we report two complementary pincer nickel platforms that serve as metalloligands to stabilize well-defined multinuclear aggregates of sodium and potassium alkoxides. The reaction of a POCOP–NiBr pincer complex with MeLi or NaOtBu led to unexpected double C–O bond cleavage of the pincer framework, generating anionic oxygen-rich fragments that assembled into a zwitterionic trinuclear lithium complex {(η3-allyl)Ni}2(μ,κP:κO-iPr2PO)4[Li3(Br)(κO-iPr2P(O)Me)] (1) and a hexanuclear sodium cluster {(η3-allyl)Ni}2(μ,κP:κO-iPr2PO)4[Na6(μ4-OtBu)2(μ-OtBu)2(μ-OtBuH)2] (2). In stark contrast, the unsymmetrical complex (κN,κC,κN′-NCN)NiBr (3) reacts with KOtBu to form a centrosymmetric trinickel species {(κN,κC,κN′-NCN:η4-Ar,η4-Ar)Ni(μ3-O)K2}2Ni(μ3-OtBu)4 (4) bridged by four KOtBu moieties, in which the NCN ligand framework remains intact. In 4, the central Ni adopts a distorted tetrahedral geometry coordinated by four oxygen atoms, while each potassium center completes its coordination sphere through three oxygen atoms and an η4-interaction with a pendant phenyl group, revealing a rare κK,κO bridging mode for KOtBu. Comprehensive single-crystal X-ray diffraction analyses confirm all structures. These results demonstrate the capacity of pincer nickel halides to stabilize otherwise elusive alkali metal alkoxide aggregates and provide new insights into the ligand-directed structural diversity of these important reagents.
SN - 2470-1343
ER -