Reaction of an osmium(vi) nitrido complex with enamines generated in situ from ketones and anilines

Lei Wang; Li-Xin Wang; Zhao-Long Liu; Fang Xu; Rui-Yue Qi; Wai-Lun Man; Jing Xiang; Ji-Yan Liu; Tai-Chu Lau

doi:10.1039/d5dt01334h

Reaction of an osmium(vi) nitrido complex with enamines generated in situ from ketones and anilines

Lei Wang (Co-first Author)
, Li-Xin Wang (Co-first Author)
, Zhao-Long Liu
, Fang Xu
, Rui-Yue Qi
, Wai-Lun Man
, Jing Xiang^*
, Ji-Yan Liu
, Tai-Chu Lau^*

^*Corresponding author for this work

Department of Chemistry

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

1 Citation (Scopus)

Abstract

The reaction of [Os^VI(N)(L)(CN)₃]⁻ (OsN, HL = 2-(2-hydroxy-5-nitrophenyl)-benzoxazole) with a mixture of acetone and 2,4,6-trimethylaniline (MesNH₂) affords [Os^III(L)(CN)₃(L¹)]⁻ (L¹ = N-mesityl-2-(mesitylimino)propanimidamide), where L¹ is derived from the combination of an acetone molecule, a nitrido ligand, and two MesNH₂ units. The reaction of OsN with acetone and the less bulky aniline gives [Os^III(L)(CN)₃(L³)]⁻ (L³ = 1,3-diphenylguanidine) and phenylacetamide, where L³ is derived from the combination of three anilines, one acetone, and the nitrido ligand; this reaction results in C-C bond cleavage of acetone. C-C bond cleavage of ketone also occurs in the reaction of OsN with 2-butanone and aniline. Mechanistic studies indicate that the initial step in these reactions is the condensation of the ketone and the amine to give an enamine, which then undergoes nucleophilic addition to Os ≡ N. © 2025 The Royal Society of Chemistry.

Original language	English
Pages (from-to)	14052-14058
Number of pages	7
Journal	Dalton Transactions
Volume	54
Issue number	37
Online published	19 Aug 2025
DOIs	https://doi.org/10.1039/d5dt01334h
Publication status	Published - 7 Oct 2025

Funding

This work was supported by the National Natural Science Foundation of China (22371092), the Excellent Discipline Cultivation Project by JHUN (2023XKZ038), the Natural Science Foundation of Anhui Province (2008085QD173), the Open Project of Hebei Key Laboratory of Heterocyclic Compounds (No. KF202402) and \u201CLaboratory for Synthetic Chemistry and Chemical Biology\u201D under the Health@InnoHK Program launched by Innovation and Technology Commission, The Government of Hong Kong Special Administrative Region of the People's Republic of China.

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@article{5772ea5f890a4ea5b947e6f74585ee5a,

title = "Reaction of an osmium(vi) nitrido complex with enamines generated in situ from ketones and anilines",

abstract = "The reaction of [OsVI(N)(L)(CN)3]− (OsN, HL = 2-(2-hydroxy-5-nitrophenyl)-benzoxazole) with a mixture of acetone and 2,4,6-trimethylaniline (MesNH2) affords [OsIII(L)(CN)3(L1)]− (L1 = N-mesityl-2-(mesitylimino)propanimidamide), where L1 is derived from the combination of an acetone molecule, a nitrido ligand, and two MesNH2 units. The reaction of OsN with acetone and the less bulky aniline gives [OsIII(L)(CN)3(L3)]− (L3 = 1,3-diphenylguanidine) and phenylacetamide, where L3 is derived from the combination of three anilines, one acetone, and the nitrido ligand; this reaction results in C-C bond cleavage of acetone. C-C bond cleavage of ketone also occurs in the reaction of OsN with 2-butanone and aniline. Mechanistic studies indicate that the initial step in these reactions is the condensation of the ketone and the amine to give an enamine, which then undergoes nucleophilic addition to Os ≡ N. {\textcopyright} 2025 The Royal Society of Chemistry.",

author = "Lei Wang and Li-Xin Wang and Zhao-Long Liu and Fang Xu and Rui-Yue Qi and Wai-Lun Man and Jing Xiang and Ji-Yan Liu and Tai-Chu Lau",

year = "2025",

month = oct,

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doi = "10.1039/d5dt01334h",

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TY - JOUR

T1 - Reaction of an osmium(vi) nitrido complex with enamines generated in situ from ketones and anilines

AU - Wang, Lei

AU - Wang, Li-Xin

AU - Liu, Zhao-Long

AU - Xu, Fang

AU - Qi, Rui-Yue

AU - Man, Wai-Lun

AU - Xiang, Jing

AU - Liu, Ji-Yan

AU - Lau, Tai-Chu

PY - 2025/10/7

Y1 - 2025/10/7

N2 - The reaction of [OsVI(N)(L)(CN)3]− (OsN, HL = 2-(2-hydroxy-5-nitrophenyl)-benzoxazole) with a mixture of acetone and 2,4,6-trimethylaniline (MesNH2) affords [OsIII(L)(CN)3(L1)]− (L1 = N-mesityl-2-(mesitylimino)propanimidamide), where L1 is derived from the combination of an acetone molecule, a nitrido ligand, and two MesNH2 units. The reaction of OsN with acetone and the less bulky aniline gives [OsIII(L)(CN)3(L3)]− (L3 = 1,3-diphenylguanidine) and phenylacetamide, where L3 is derived from the combination of three anilines, one acetone, and the nitrido ligand; this reaction results in C-C bond cleavage of acetone. C-C bond cleavage of ketone also occurs in the reaction of OsN with 2-butanone and aniline. Mechanistic studies indicate that the initial step in these reactions is the condensation of the ketone and the amine to give an enamine, which then undergoes nucleophilic addition to Os ≡ N. © 2025 The Royal Society of Chemistry.

AB - The reaction of [OsVI(N)(L)(CN)3]− (OsN, HL = 2-(2-hydroxy-5-nitrophenyl)-benzoxazole) with a mixture of acetone and 2,4,6-trimethylaniline (MesNH2) affords [OsIII(L)(CN)3(L1)]− (L1 = N-mesityl-2-(mesitylimino)propanimidamide), where L1 is derived from the combination of an acetone molecule, a nitrido ligand, and two MesNH2 units. The reaction of OsN with acetone and the less bulky aniline gives [OsIII(L)(CN)3(L3)]− (L3 = 1,3-diphenylguanidine) and phenylacetamide, where L3 is derived from the combination of three anilines, one acetone, and the nitrido ligand; this reaction results in C-C bond cleavage of acetone. C-C bond cleavage of ketone also occurs in the reaction of OsN with 2-butanone and aniline. Mechanistic studies indicate that the initial step in these reactions is the condensation of the ketone and the amine to give an enamine, which then undergoes nucleophilic addition to Os ≡ N. © 2025 The Royal Society of Chemistry.

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U2 - 10.1039/d5dt01334h

DO - 10.1039/d5dt01334h

M3 - RGC 21 - Publication in refereed journal

C2 - 40891415

SN - 1477-9226

VL - 54

SP - 14052

EP - 14058

JO - Dalton Transactions

JF - Dalton Transactions

IS - 37

ER -

Reaction of an osmium(vi) nitrido complex with enamines generated in situ from ketones and anilines

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