Synthesis and structure of a bismuth(III)/chromium(VI) oxo cluster containing a Bi 4Cr 4O 12 core

Guo Cang Wang; Xiao Yi Yi; Ian D. Williams; Wa Hung Leung

doi:10.1021/ic201351j

Synthesis and structure of a bismuth(III)/chromium(VI) oxo cluster containing a Bi ₄Cr ₄O ₁₂ core

Guo Cang Wang, Xiao Yi Yi, 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

Bismuth(III) compounds containing the Kläui's oxygen tripodal ligand [CpCo{P(O)(OEt) ₂} ₃] ^- (L _OEt ^-) have been synthesized, and their interactions with dichromate in aqueous media were studied. The treatment of Bi ₅O(OH) ₉(NO ₃) ₄ with NaL _OEt in water afforded [L _OEtBi(NO ₃) ₂] ₂ (1), whereas that of BiCl ₃ with NaL _OEt in CH ₂Cl ₂ yielded L _OEtBiCl ₂ (2). Chloride abstraction of 2 with AgX afforded [L _OEtBiX ₂] ₂ [X ^- = triflate (OTf ^-) (3), tosylate (OTs ^-) (4)]. In aqueous solutions at pH > 4, 4 underwent ligand redistribution to give the bis(tripod) complex [(L _OEt) ₂Bi(H ₂O)][OTs] (5). The treatment of 4 with Na ₂Cr ₂O ₇ in acetone/water afforded the Bi(III)/Cr(VI) oxo cluster [(L _OEt) ₄Bi ₄(μ ₃-CrO ₄) ₂(μ ₃-Cr ₂O ₇) ₂] (6) containing a unique Bi ₄Cr ₄O ₁₂ oxometallic core. Compound 6 oxidized benzyl alcohol to give ca. 6 equiv of benzaldehyde. The reaction between 2 and CrO ₃ yielded [L _OEtBi(OCrO ₂Cl)] ₂(μ-Cl) ₂ (7). The crystal structures of complexes 4-7 have been determined.

Original language	English
Pages (from-to)	9141-9146
Number of pages	6
Journal	Inorganic Chemistry
Volume	50
Issue number	18
DOIs	https://doi.org/10.1021/ic201351j
Publication status	Published - 19 Sept 2011

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@article{1415c6a3807e4af9b77b015e6a36fe65,

title = "Synthesis and structure of a bismuth(III)/chromium(VI) oxo cluster containing a Bi 4Cr 4O 12 core",

abstract = "Bismuth(III) compounds containing the Kl{\"a}ui's oxygen tripodal ligand [CpCo\{P(O)(OEt) 2\} 3] - (L OEt -) have been synthesized, and their interactions with dichromate in aqueous media were studied. The treatment of Bi 5O(OH) 9(NO 3) 4 with NaL OEt in water afforded [L OEtBi(NO 3) 2] 2 (1), whereas that of BiCl 3 with NaL OEt in CH 2Cl 2 yielded L OEtBiCl 2 (2). Chloride abstraction of 2 with AgX afforded [L OEtBiX 2] 2 [X - = triflate (OTf -) (3), tosylate (OTs -) (4)]. In aqueous solutions at pH > 4, 4 underwent ligand redistribution to give the bis(tripod) complex [(L OEt) 2Bi(H 2O)][OTs] (5). The treatment of 4 with Na 2Cr 2O 7 in acetone/water afforded the Bi(III)/Cr(VI) oxo cluster [(L OEt) 4Bi 4(μ 3-CrO 4) 2(μ 3-Cr 2O 7) 2] (6) containing a unique Bi 4Cr 4O 12 oxometallic core. Compound 6 oxidized benzyl alcohol to give ca. 6 equiv of benzaldehyde. The reaction between 2 and CrO 3 yielded [L OEtBi(OCrO 2Cl)] 2(μ-Cl) 2 (7). The crystal structures of complexes 4-7 have been determined.",

author = "Wang, \{Guo Cang\} and Yi, \{Xiao Yi\} and Williams, \{Ian D.\} and Leung, \{Wa Hung\}",

year = "2011",

month = sep,

day = "19",

doi = "10.1021/ic201351j",

language = "English",

volume = "50",

pages = "9141--9146",

journal = "Inorganic Chemistry",

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T1 - Synthesis and structure of a bismuth(III)/chromium(VI) oxo cluster containing a Bi 4Cr 4O 12 core

AU - Wang, Guo Cang

AU - Yi, Xiao Yi

AU - Williams, Ian D.

AU - Leung, Wa Hung

PY - 2011/9/19

Y1 - 2011/9/19

N2 - Bismuth(III) compounds containing the Kläui's oxygen tripodal ligand [CpCo{P(O)(OEt) 2} 3] - (L OEt -) have been synthesized, and their interactions with dichromate in aqueous media were studied. The treatment of Bi 5O(OH) 9(NO 3) 4 with NaL OEt in water afforded [L OEtBi(NO 3) 2] 2 (1), whereas that of BiCl 3 with NaL OEt in CH 2Cl 2 yielded L OEtBiCl 2 (2). Chloride abstraction of 2 with AgX afforded [L OEtBiX 2] 2 [X - = triflate (OTf -) (3), tosylate (OTs -) (4)]. In aqueous solutions at pH > 4, 4 underwent ligand redistribution to give the bis(tripod) complex [(L OEt) 2Bi(H 2O)][OTs] (5). The treatment of 4 with Na 2Cr 2O 7 in acetone/water afforded the Bi(III)/Cr(VI) oxo cluster [(L OEt) 4Bi 4(μ 3-CrO 4) 2(μ 3-Cr 2O 7) 2] (6) containing a unique Bi 4Cr 4O 12 oxometallic core. Compound 6 oxidized benzyl alcohol to give ca. 6 equiv of benzaldehyde. The reaction between 2 and CrO 3 yielded [L OEtBi(OCrO 2Cl)] 2(μ-Cl) 2 (7). The crystal structures of complexes 4-7 have been determined.

AB - Bismuth(III) compounds containing the Kläui's oxygen tripodal ligand [CpCo{P(O)(OEt) 2} 3] - (L OEt -) have been synthesized, and their interactions with dichromate in aqueous media were studied. The treatment of Bi 5O(OH) 9(NO 3) 4 with NaL OEt in water afforded [L OEtBi(NO 3) 2] 2 (1), whereas that of BiCl 3 with NaL OEt in CH 2Cl 2 yielded L OEtBiCl 2 (2). Chloride abstraction of 2 with AgX afforded [L OEtBiX 2] 2 [X - = triflate (OTf -) (3), tosylate (OTs -) (4)]. In aqueous solutions at pH > 4, 4 underwent ligand redistribution to give the bis(tripod) complex [(L OEt) 2Bi(H 2O)][OTs] (5). The treatment of 4 with Na 2Cr 2O 7 in acetone/water afforded the Bi(III)/Cr(VI) oxo cluster [(L OEt) 4Bi 4(μ 3-CrO 4) 2(μ 3-Cr 2O 7) 2] (6) containing a unique Bi 4Cr 4O 12 oxometallic core. Compound 6 oxidized benzyl alcohol to give ca. 6 equiv of benzaldehyde. The reaction between 2 and CrO 3 yielded [L OEtBi(OCrO 2Cl)] 2(μ-Cl) 2 (7). The crystal structures of complexes 4-7 have been determined.

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U2 - 10.1021/ic201351j

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C2 - 21812444

SN - 0020-1669

VL - 50

SP - 9141

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 18

ER -

Synthesis and structure of a bismuth(III)/chromium(VI) oxo cluster containing a Bi ₄Cr ₄O ₁₂ core

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