Reduction of Ketones and Coupling of Ketyls by a Zn-Zn-Bonded Compound

Rui Liu; Yao Qu; Zhenzhou Sun; Li Yang; Zhixian Xi; Ben Dong; Meng Guo; Igor L. Fedushkin; Xiao Juan Yang

doi:10.1021/acs.inorgchem.4c01669

Reduction of Ketones and Coupling of Ketyls by a Zn-Zn-Bonded Compound

Rui Liu, Yao Qu, Zhenzhou Sun, Li Yang, Zhixian Xi, Ben Dong, Meng Guo, Igor L. Fedushkin, Xiao Juan Yang^*

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

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

Abstract

The α-diimine-ligated Zn-Zn-bonded compound [K(THF)₂]₂[LZn-ZnL] (1, L = [(2,6-iPr₂C₆H₃)NC(Me)]₂^2-) displays diverse reactivities toward a variety of ketones. In the reaction of 1 with benzophenone or 4,4′-di-tert-butylbenzophenone, a multielectron transfer process was observed to give bimetallic (Zn/K) complexes with both ketyl radical fragments and C-C coupled pinacolate moieties (products 2 and 3). In contrast, treating 1 with 9-fluorenone only afforded pinacolate complex 5. Moreover, the reactions of 1 with N- or O-heterocycle-functionalized ketones, i.e., di(2-pyridyl)ketone, 2,2-pyrrolidinone, 9-xanthenone, or 10-methyl-9(10H)-acridone, were also carried out. Besides different transformations of the ketone moiety, the heteroatoms (nitrogen or oxygen) are also involved in coordination with zinc or potassium ions, yielding discrete aggregates or polymeric structures of products 6-9.

Original language	English
Pages (from-to)	13558-13567
Number of pages	10
Journal	Inorganic Chemistry
Volume	63
Issue number	29
DOIs	https://doi.org/10.1021/acs.inorgchem.4c01669
Publication status	Published - 22 Jul 2024

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@article{f1f540a8951f4c85b4fbe5d832e062bd,

title = "Reduction of Ketones and Coupling of Ketyls by a Zn-Zn-Bonded Compound",

abstract = "The α-diimine-ligated Zn-Zn-bonded compound [K(THF)2]2[LZn-ZnL] (1, L = [(2,6-iPr2C6H3)NC(Me)]22-) displays diverse reactivities toward a variety of ketones. In the reaction of 1 with benzophenone or 4,4′-di-tert-butylbenzophenone, a multielectron transfer process was observed to give bimetallic (Zn/K) complexes with both ketyl radical fragments and C-C coupled pinacolate moieties (products 2 and 3). In contrast, treating 1 with 9-fluorenone only afforded pinacolate complex 5. Moreover, the reactions of 1 with N- or O-heterocycle-functionalized ketones, i.e., di(2-pyridyl)ketone, 2,2-pyrrolidinone, 9-xanthenone, or 10-methyl-9(10H)-acridone, were also carried out. Besides different transformations of the ketone moiety, the heteroatoms (nitrogen or oxygen) are also involved in coordination with zinc or potassium ions, yielding discrete aggregates or polymeric structures of products 6-9.",

author = "Rui Liu and Yao Qu and Zhenzhou Sun and Li Yang and Zhixian Xi and Ben Dong and Meng Guo and Fedushkin, {Igor L.} and Yang, {Xiao Juan}",

note = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society.",

year = "2024",

month = jul,

day = "22",

doi = "10.1021/acs.inorgchem.4c01669",

language = "English",

volume = "63",

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journal = "Inorganic Chemistry",

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T1 - Reduction of Ketones and Coupling of Ketyls by a Zn-Zn-Bonded Compound

AU - Liu, Rui

AU - Qu, Yao

AU - Sun, Zhenzhou

AU - Yang, Li

AU - Xi, Zhixian

AU - Dong, Ben

AU - Guo, Meng

AU - Fedushkin, Igor L.

AU - Yang, Xiao Juan

PY - 2024/7/22

Y1 - 2024/7/22

N2 - The α-diimine-ligated Zn-Zn-bonded compound [K(THF)2]2[LZn-ZnL] (1, L = [(2,6-iPr2C6H3)NC(Me)]22-) displays diverse reactivities toward a variety of ketones. In the reaction of 1 with benzophenone or 4,4′-di-tert-butylbenzophenone, a multielectron transfer process was observed to give bimetallic (Zn/K) complexes with both ketyl radical fragments and C-C coupled pinacolate moieties (products 2 and 3). In contrast, treating 1 with 9-fluorenone only afforded pinacolate complex 5. Moreover, the reactions of 1 with N- or O-heterocycle-functionalized ketones, i.e., di(2-pyridyl)ketone, 2,2-pyrrolidinone, 9-xanthenone, or 10-methyl-9(10H)-acridone, were also carried out. Besides different transformations of the ketone moiety, the heteroatoms (nitrogen or oxygen) are also involved in coordination with zinc or potassium ions, yielding discrete aggregates or polymeric structures of products 6-9.

AB - The α-diimine-ligated Zn-Zn-bonded compound [K(THF)2]2[LZn-ZnL] (1, L = [(2,6-iPr2C6H3)NC(Me)]22-) displays diverse reactivities toward a variety of ketones. In the reaction of 1 with benzophenone or 4,4′-di-tert-butylbenzophenone, a multielectron transfer process was observed to give bimetallic (Zn/K) complexes with both ketyl radical fragments and C-C coupled pinacolate moieties (products 2 and 3). In contrast, treating 1 with 9-fluorenone only afforded pinacolate complex 5. Moreover, the reactions of 1 with N- or O-heterocycle-functionalized ketones, i.e., di(2-pyridyl)ketone, 2,2-pyrrolidinone, 9-xanthenone, or 10-methyl-9(10H)-acridone, were also carried out. Besides different transformations of the ketone moiety, the heteroatoms (nitrogen or oxygen) are also involved in coordination with zinc or potassium ions, yielding discrete aggregates or polymeric structures of products 6-9.

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U2 - 10.1021/acs.inorgchem.4c01669

DO - 10.1021/acs.inorgchem.4c01669

M3 - Article

AN - SCOPUS:85198193578

SN - 0020-1669

VL - 63

SP - 13558

EP - 13567

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 29

ER -

Reduction of Ketones and Coupling of Ketyls by a Zn-Zn-Bonded Compound

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