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
, Li Xin Wang
, 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: Contribution to journal › Journal article › 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.

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

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@article{f607323f42444dbc965bfd73f18ec9ec,

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.",

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

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2025. Funding Information: 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 “Laboratory for Synthetic Chemistry and Chemical Biology” under the Health@InnoHK Program launched by Innovation and Technology Commission, The Government of Hong Kong Special Administrative Region of the People{\textquoteright}s Republic of China.",

year = "2025",

month = oct,

day = "7",

doi = "10.1039/d5dt01334h",

language = "English",

volume = "54",

pages = "14052--14058",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "37",

}

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

N1 - Publisher Copyright: © The Royal Society of Chemistry 2025. Funding Information: 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 “Laboratory for Synthetic Chemistry and Chemical Biology” 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.

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.

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.

UR - https://www.scopus.com/pages/publications/105016754137

U2 - 10.1039/d5dt01334h

DO - 10.1039/d5dt01334h

M3 - Journal article

C2 - 40891415

AN - SCOPUS:105016754137

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

Abstract

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