Syntheses and electrochemistry of imidochromium(v) compounds. Crystal structure of [PPh4][Cr(NBut)Cl4(OH2)]

Wa Hung Leung; Man Ching Wu; Kwok Yin Wong; Yu Wang

doi:10.1039/DT9940001659

Syntheses and electrochemistry of imidochromium(v) compounds. Crystal structure of [PPh₄][Cr(NBu^t)Cl₄(OH₂)]

Wa Hung Leung, Man Ching Wu, Kwok Yin Wong, Yu Wang

Research output: Journal article publication › Journal article › Academic research › peer-review

18 Citations (Scopus)

Abstract

Reactions of [Cr(NBut)Cl3(dme)] (dme = 1,2-dimethoxyethane) or [PPh4][Cr(NBut)Cl4] with Tl(C5H5) and NaL′ {L′ = (η-C5H5)Co[PO(OEt)2]3} gave respective paramagnetic (μeffca. 1.7 μB) half-sandwich imidochromium(V) compounds [CrL(NBut)Cl2] (L = η-C5H51 or L′ 2). The structure of [PPh4][Cr-(NBut)Cl4(OH2)] has been established by X-ray crystallography. The [Cr(NBut)Cl4(OH2)]-anion has an octahedral geometry with Cr-N (imido) 1.619(3) Å. Treatment of [Cr(NBut)(L)Cl] [H2L = N,N′-bis(salicylidene)ethane-1,2-diamine or its 3,5-But2derivative] with AgBF4afforded cationic imidochromium(V) Schiff-base compounds [Cr(NBut)L]BF4. Reactions of the imidochromium(V) compounds with PPh3at reflux or on irradiation with UV light gave Ph3P=NButand CrIII. Cyclic voltammetry of the imidochromium(V) compounds showed in most cases irreversible oxidation and reduction waves, which are attributed to oxidation and reduction of CrV.

Original language	English
Pages (from-to)	1659-1663
Number of pages	5
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	11
DOIs	https://doi.org/10.1039/DT9940001659
Publication status	Published - 1 Dec 1994

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Chemistry(all)

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@article{5965313e2c704002979539ef4fd9fc46,

title = "Syntheses and electrochemistry of imidochromium(v) compounds. Crystal structure of [PPh4][Cr(NBut)Cl4(OH2)]",

abstract = "Reactions of [Cr(NBut)Cl3(dme)] (dme = 1,2-dimethoxyethane) or [PPh4][Cr(NBut)Cl4] with Tl(C5H5) and NaL′ {L′ = (η-C5H5)Co[PO(OEt)2]3} gave respective paramagnetic (μeffca. 1.7 μB) half-sandwich imidochromium(V) compounds [CrL(NBut)Cl2] (L = η-C5H51 or L′ 2). The structure of [PPh4][Cr-(NBut)Cl4(OH2)] has been established by X-ray crystallography. The [Cr(NBut)Cl4(OH2)]-anion has an octahedral geometry with Cr-N (imido) 1.619(3) {\AA}. Treatment of [Cr(NBut)(L)Cl] [H2L = N,N′-bis(salicylidene)ethane-1,2-diamine or its 3,5-But2derivative] with AgBF4afforded cationic imidochromium(V) Schiff-base compounds [Cr(NBut)L]BF4. Reactions of the imidochromium(V) compounds with PPh3at reflux or on irradiation with UV light gave Ph3P=NButand CrIII. Cyclic voltammetry of the imidochromium(V) compounds showed in most cases irreversible oxidation and reduction waves, which are attributed to oxidation and reduction of CrV.",

author = "Leung, {Wa Hung} and Wu, {Man Ching} and Wong, {Kwok Yin} and Yu Wang",

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AU - Wang, Yu

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N2 - Reactions of [Cr(NBut)Cl3(dme)] (dme = 1,2-dimethoxyethane) or [PPh4][Cr(NBut)Cl4] with Tl(C5H5) and NaL′ {L′ = (η-C5H5)Co[PO(OEt)2]3} gave respective paramagnetic (μeffca. 1.7 μB) half-sandwich imidochromium(V) compounds [CrL(NBut)Cl2] (L = η-C5H51 or L′ 2). The structure of [PPh4][Cr-(NBut)Cl4(OH2)] has been established by X-ray crystallography. The [Cr(NBut)Cl4(OH2)]-anion has an octahedral geometry with Cr-N (imido) 1.619(3) Å. Treatment of [Cr(NBut)(L)Cl] [H2L = N,N′-bis(salicylidene)ethane-1,2-diamine or its 3,5-But2derivative] with AgBF4afforded cationic imidochromium(V) Schiff-base compounds [Cr(NBut)L]BF4. Reactions of the imidochromium(V) compounds with PPh3at reflux or on irradiation with UV light gave Ph3P=NButand CrIII. Cyclic voltammetry of the imidochromium(V) compounds showed in most cases irreversible oxidation and reduction waves, which are attributed to oxidation and reduction of CrV.

AB - Reactions of [Cr(NBut)Cl3(dme)] (dme = 1,2-dimethoxyethane) or [PPh4][Cr(NBut)Cl4] with Tl(C5H5) and NaL′ {L′ = (η-C5H5)Co[PO(OEt)2]3} gave respective paramagnetic (μeffca. 1.7 μB) half-sandwich imidochromium(V) compounds [CrL(NBut)Cl2] (L = η-C5H51 or L′ 2). The structure of [PPh4][Cr-(NBut)Cl4(OH2)] has been established by X-ray crystallography. The [Cr(NBut)Cl4(OH2)]-anion has an octahedral geometry with Cr-N (imido) 1.619(3) Å. Treatment of [Cr(NBut)(L)Cl] [H2L = N,N′-bis(salicylidene)ethane-1,2-diamine or its 3,5-But2derivative] with AgBF4afforded cationic imidochromium(V) Schiff-base compounds [Cr(NBut)L]BF4. Reactions of the imidochromium(V) compounds with PPh3at reflux or on irradiation with UV light gave Ph3P=NButand CrIII. Cyclic voltammetry of the imidochromium(V) compounds showed in most cases irreversible oxidation and reduction waves, which are attributed to oxidation and reduction of CrV.

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Syntheses and electrochemistry of imidochromium(v) compounds. Crystal structure of [PPh₄][Cr(NBu^t)Cl₄(OH₂)]

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