Synthesis, structures, and oxidation of iridium(III) alkyl compounds containing thiolate and dithiolate ligands

Ka Wang Chan; Yiu Keung Sau; Qian Feng Zhang; Wai Yeung Wong; Ian D. Williams; Wa Hung Leung

doi:10.1002/ejic.200800460

Synthesis, structures, and oxidation of iridium(III) alkyl compounds containing thiolate and dithiolate ligands

Ka Wang Chan, Yiu Keung Sau, Qian Feng Zhang, Wai Yeung Wong, Ian D. Williams, Wa Hung Leung^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal article › peer-review

8 Citations (Scopus)

Abstract

Treatment of [Ir(dtbpy){CH₂CMe₂C^c ₆H₄(Ir-C^c)}(C₆H₄tBu-2)] (1) (dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridyl) with the dichalcogenides R₂Q₂ in refluxing toluene afforded the chalcogenolate-bridged dinuclear complexes [Ir(dtbpy)-{CH₂CMe ₂C⁶₆H₄(Ir-C^c)}] ₂(μ-QR)₂ [RQ = pTolS (2), PhSe (3)]. Similarly, heating a solution of [Rh(dtbpy){CH₂CMe₂-C^c ₆H₄(Ir-C^c)}(CH₂CMe₂Ph)] and p-tolyl sulfide in toluene at reflux gave [Rh(dtbpy){CH₂CMe ₂C^c₆H₄(Ir-C^c)}] ₂(μ-SpTol)₂ (4). Treatment of [Ir(dtbpy)(CH ₂CMe₂Ph)Cl]₂(μ-Cl)₂ with Na(Sxyl) (xyl = 2,6-dimethylphenyl) and Na₂(S∧S) afforded [Ir(dtbpy)(CH₂CMe₂Ph)(Sxyl)₂]₂ (5) and [Ir(dtbpy)-(CH₂CMe₂Ph)(S∧S)]₂ {S∧S₂- = maleonitriledithiolate (6), toluene-3,4-dithiolate (7), benzene-1,2-dithiolate (8)}. Oxidation of compound 8 with AgOTf (OTf- = triflate) resulted in dimerization of the bdt^2- ligand by S-S bond formation and the isolation of [Ir₂(dtbpy)₂(CH ₂Me₂Ph)₂{(bdt)₂}][OTf]₂ (9). The solid-state structures of compounds 2, 3, 4, 7, and 9 were determined.

Original language	English
Pages (from-to)	4353-4359
Number of pages	7
Journal	European Journal of Inorganic Chemistry
Issue number	28
DOIs	https://doi.org/10.1002/ejic.200800460
Publication status	Published - Oct 2008

Scopus Subject Areas

Inorganic Chemistry

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Iridium
Oxidation
S ligands

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10.1002/ejic.200800460

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@article{454596392d86403cbb7c1320a1490ff2,

title = "Synthesis, structures, and oxidation of iridium(III) alkyl compounds containing thiolate and dithiolate ligands",

abstract = "Treatment of [Ir(dtbpy){CH2CMe2Cc 6H4(Ir-Cc)}(C6H4tBu-2)] (1) (dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridyl) with the dichalcogenides R2Q2 in refluxing toluene afforded the chalcogenolate-bridged dinuclear complexes [Ir(dtbpy)-{CH2CMe 2C66H4(Ir-Cc)}] 2(μ-QR)2 [RQ = pTolS (2), PhSe (3)]. Similarly, heating a solution of [Rh(dtbpy){CH2CMe2-Cc 6H4(Ir-Cc)}(CH2CMe2Ph)] and p-tolyl sulfide in toluene at reflux gave [Rh(dtbpy){CH2CMe 2Cc6H4(Ir-Cc)}] 2(μ-SpTol)2 (4). Treatment of [Ir(dtbpy)(CH 2CMe2Ph)Cl]2(μ-Cl)2 with Na(Sxyl) (xyl = 2,6-dimethylphenyl) and Na2(S∧S) afforded [Ir(dtbpy)(CH2CMe2Ph)(Sxyl)2]2 (5) and [Ir(dtbpy)-(CH2CMe2Ph)(S∧S)]2 {S∧S2- = maleonitriledithiolate (6), toluene-3,4-dithiolate (7), benzene-1,2-dithiolate (8)}. Oxidation of compound 8 with AgOTf (OTf- = triflate) resulted in dimerization of the bdt2- ligand by S-S bond formation and the isolation of [Ir2(dtbpy)2(CH 2Me2Ph)2{(bdt)2}][OTf]2 (9). The solid-state structures of compounds 2, 3, 4, 7, and 9 were determined.",

keywords = "Iridium, Oxidation, S ligands",

author = "Chan, {Ka Wang} and Sau, {Yiu Keung} and Zhang, {Qian Feng} and Wong, {Wai Yeung} and Williams, {Ian D.} and Leung, {Wa Hung}",

year = "2008",

month = oct,

doi = "10.1002/ejic.200800460",

language = "English",

pages = "4353--4359",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag",

number = "28",

}

TY - JOUR

T1 - Synthesis, structures, and oxidation of iridium(III) alkyl compounds containing thiolate and dithiolate ligands

AU - Chan, Ka Wang

AU - Sau, Yiu Keung

AU - Zhang, Qian Feng

AU - Wong, Wai Yeung

AU - Williams, Ian D.

AU - Leung, Wa Hung

PY - 2008/10

Y1 - 2008/10

N2 - Treatment of [Ir(dtbpy){CH2CMe2Cc 6H4(Ir-Cc)}(C6H4tBu-2)] (1) (dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridyl) with the dichalcogenides R2Q2 in refluxing toluene afforded the chalcogenolate-bridged dinuclear complexes [Ir(dtbpy)-{CH2CMe 2C66H4(Ir-Cc)}] 2(μ-QR)2 [RQ = pTolS (2), PhSe (3)]. Similarly, heating a solution of [Rh(dtbpy){CH2CMe2-Cc 6H4(Ir-Cc)}(CH2CMe2Ph)] and p-tolyl sulfide in toluene at reflux gave [Rh(dtbpy){CH2CMe 2Cc6H4(Ir-Cc)}] 2(μ-SpTol)2 (4). Treatment of [Ir(dtbpy)(CH 2CMe2Ph)Cl]2(μ-Cl)2 with Na(Sxyl) (xyl = 2,6-dimethylphenyl) and Na2(S∧S) afforded [Ir(dtbpy)(CH2CMe2Ph)(Sxyl)2]2 (5) and [Ir(dtbpy)-(CH2CMe2Ph)(S∧S)]2 {S∧S2- = maleonitriledithiolate (6), toluene-3,4-dithiolate (7), benzene-1,2-dithiolate (8)}. Oxidation of compound 8 with AgOTf (OTf- = triflate) resulted in dimerization of the bdt2- ligand by S-S bond formation and the isolation of [Ir2(dtbpy)2(CH 2Me2Ph)2{(bdt)2}][OTf]2 (9). The solid-state structures of compounds 2, 3, 4, 7, and 9 were determined.

AB - Treatment of [Ir(dtbpy){CH2CMe2Cc 6H4(Ir-Cc)}(C6H4tBu-2)] (1) (dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridyl) with the dichalcogenides R2Q2 in refluxing toluene afforded the chalcogenolate-bridged dinuclear complexes [Ir(dtbpy)-{CH2CMe 2C66H4(Ir-Cc)}] 2(μ-QR)2 [RQ = pTolS (2), PhSe (3)]. Similarly, heating a solution of [Rh(dtbpy){CH2CMe2-Cc 6H4(Ir-Cc)}(CH2CMe2Ph)] and p-tolyl sulfide in toluene at reflux gave [Rh(dtbpy){CH2CMe 2Cc6H4(Ir-Cc)}] 2(μ-SpTol)2 (4). Treatment of [Ir(dtbpy)(CH 2CMe2Ph)Cl]2(μ-Cl)2 with Na(Sxyl) (xyl = 2,6-dimethylphenyl) and Na2(S∧S) afforded [Ir(dtbpy)(CH2CMe2Ph)(Sxyl)2]2 (5) and [Ir(dtbpy)-(CH2CMe2Ph)(S∧S)]2 {S∧S2- = maleonitriledithiolate (6), toluene-3,4-dithiolate (7), benzene-1,2-dithiolate (8)}. Oxidation of compound 8 with AgOTf (OTf- = triflate) resulted in dimerization of the bdt2- ligand by S-S bond formation and the isolation of [Ir2(dtbpy)2(CH 2Me2Ph)2{(bdt)2}][OTf]2 (9). The solid-state structures of compounds 2, 3, 4, 7, and 9 were determined.

KW - Iridium

KW - Oxidation

KW - S ligands

UR - http://www.scopus.com/inward/record.url?scp=53549107492&partnerID=8YFLogxK

U2 - 10.1002/ejic.200800460

DO - 10.1002/ejic.200800460

M3 - Journal article

AN - SCOPUS:53549107492

SN - 1434-1948

SP - 4353

EP - 4359

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 28

ER -

Synthesis, structures, and oxidation of iridium(III) alkyl compounds containing thiolate and dithiolate ligands

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