Synthesis and electrochemistry of dialkylosmium-(IV) and -(V) porphyrins. Crystal structure of [Os(ttp)(CH2SiMe3)2] [H2ttp = 5,10,15,20-tetra(p-tolyl)porphyrin]

Wa Hung Leung; Tom S.M. Hun; Kwok Yin Wong; Wing Tak Wong

doi:10.1039/DT9940002713

Synthesis and electrochemistry of dialkylosmium-(IV) and -(V) porphyrins. Crystal structure of [Os(ttp)(CH₂SiMe₃)₂] [H₂ttp = 5,10,15,20-tetra(p-tolyl)porphyrin]

Wa Hung Leung, Tom S.M. Hun, Kwok Yin Wong, Wing Tak Wong

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

22 Citations (Scopus)

Abstract

Reaction of [Os(por)O2] [por = 5,10,15,20-tetra(p-tolyl)porphyrinate (ttp) or 2,3,7,8,12,13,17,18-octaethylporphyrinate (oep)] with thionyl chloride gave [Os(por)Cl2] in good yields. The dichloride compounds are paramagnetic with μeff ca.2.7 μB and display temperature-independent contact-shifted 1H NMR spectra. Reaction of [Os(por)Cl2] with an excess of LiR (R = Ph or Me3SiCH2) gave air-stable diamagnetic dialkyl compounds [Os(por)R2]. The structure of [Os(ttp)(CH2SiMe3)2] has been established by X-ray crystallography. Cyclic voltammograms of the diphenyl compounds exhibit reversible metal-centred OsV-OsIV and OsIV-OsIII couples. Treatment of [Os(ttp)Ph2] with CeIV or AgBF4 afforded the diphenylosmium(V) compound [Os(ttp)Ph2]BF4, which is paramagnetic with μeff ca. 1.7 μB.

Original language	English
Pages (from-to)	2713-2718
Number of pages	6
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	18
DOIs	https://doi.org/10.1039/DT9940002713
Publication status	Published - 1 Dec 1994

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Chemistry(all)

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10.1039/DT9940002713

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title = "Synthesis and electrochemistry of dialkylosmium-(IV) and -(V) porphyrins. Crystal structure of [Os(ttp)(CH2SiMe3)2] [H2ttp = 5,10,15,20-tetra(p-tolyl)porphyrin]",

abstract = "Reaction of [Os(por)O2] [por = 5,10,15,20-tetra(p-tolyl)porphyrinate (ttp) or 2,3,7,8,12,13,17,18-octaethylporphyrinate (oep)] with thionyl chloride gave [Os(por)Cl2] in good yields. The dichloride compounds are paramagnetic with μeff ca.2.7 μB and display temperature-independent contact-shifted 1H NMR spectra. Reaction of [Os(por)Cl2] with an excess of LiR (R = Ph or Me3SiCH2) gave air-stable diamagnetic dialkyl compounds [Os(por)R2]. The structure of [Os(ttp)(CH2SiMe3)2] has been established by X-ray crystallography. Cyclic voltammograms of the diphenyl compounds exhibit reversible metal-centred OsV-OsIV and OsIV-OsIII couples. Treatment of [Os(ttp)Ph2] with CeIV or AgBF4 afforded the diphenylosmium(V) compound [Os(ttp)Ph2]BF4, which is paramagnetic with μeff ca. 1.7 μB.",

author = "Leung, {Wa Hung} and Hun, {Tom S.M.} and Wong, {Kwok Yin} and Wong, {Wing Tak}",

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pages = "2713--2718",

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}

Synthesis and electrochemistry of dialkylosmium-(IV) and -(V) porphyrins. Crystal structure of [Os(ttp)(CH₂SiMe₃)₂] [H₂ttp = 5,10,15,20-tetra(p-tolyl)porphyrin]. / Leung, Wa Hung; Hun, Tom S.M.; Wong, Kwok Yin et al.

In: Journal of the Chemical Society, Dalton Transactions, No. 18, 01.12.1994, p. 2713-2718.

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

TY - JOUR

T1 - Synthesis and electrochemistry of dialkylosmium-(IV) and -(V) porphyrins. Crystal structure of [Os(ttp)(CH2SiMe3)2] [H2ttp = 5,10,15,20-tetra(p-tolyl)porphyrin]

AU - Leung, Wa Hung

AU - Hun, Tom S.M.

AU - Wong, Kwok Yin

AU - Wong, Wing Tak

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N2 - Reaction of [Os(por)O2] [por = 5,10,15,20-tetra(p-tolyl)porphyrinate (ttp) or 2,3,7,8,12,13,17,18-octaethylporphyrinate (oep)] with thionyl chloride gave [Os(por)Cl2] in good yields. The dichloride compounds are paramagnetic with μeff ca.2.7 μB and display temperature-independent contact-shifted 1H NMR spectra. Reaction of [Os(por)Cl2] with an excess of LiR (R = Ph or Me3SiCH2) gave air-stable diamagnetic dialkyl compounds [Os(por)R2]. The structure of [Os(ttp)(CH2SiMe3)2] has been established by X-ray crystallography. Cyclic voltammograms of the diphenyl compounds exhibit reversible metal-centred OsV-OsIV and OsIV-OsIII couples. Treatment of [Os(ttp)Ph2] with CeIV or AgBF4 afforded the diphenylosmium(V) compound [Os(ttp)Ph2]BF4, which is paramagnetic with μeff ca. 1.7 μB.

AB - Reaction of [Os(por)O2] [por = 5,10,15,20-tetra(p-tolyl)porphyrinate (ttp) or 2,3,7,8,12,13,17,18-octaethylporphyrinate (oep)] with thionyl chloride gave [Os(por)Cl2] in good yields. The dichloride compounds are paramagnetic with μeff ca.2.7 μB and display temperature-independent contact-shifted 1H NMR spectra. Reaction of [Os(por)Cl2] with an excess of LiR (R = Ph or Me3SiCH2) gave air-stable diamagnetic dialkyl compounds [Os(por)R2]. The structure of [Os(ttp)(CH2SiMe3)2] has been established by X-ray crystallography. Cyclic voltammograms of the diphenyl compounds exhibit reversible metal-centred OsV-OsIV and OsIV-OsIII couples. Treatment of [Os(ttp)Ph2] with CeIV or AgBF4 afforded the diphenylosmium(V) compound [Os(ttp)Ph2]BF4, which is paramagnetic with μeff ca. 1.7 μB.

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M3 - Journal article

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JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

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Synthesis and electrochemistry of dialkylosmium-(IV) and -(V) porphyrins. Crystal structure of [Os(ttp)(CH₂SiMe₃)₂] [H₂ttp = 5,10,15,20-tetra(p-tolyl)porphyrin]

Abstract

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