Reaction of [Et4N]2[TeCr(CO)5} n] (n = 2, 3) toward electrophiles: Reactivity comparison and theoretical calculations

Minghuey Shieh; Li Fang Ho; Pei Chi Chen; Miao Hsing Hsu; Hui Lung Chen; Yu Wen Guo; Yi Wen Pan; Yi Chun Lin

doi:10.1021/om700789a

Reaction of [Et₄N]₂[TeCr(CO)₅} _n] (n = 2, 3) toward electrophiles: Reactivity comparison and theoretical calculations

Minghuey Shieh^*, Li Fang Ho, Pei Chi Chen, Miao Hsing Hsu, Hui Lung Chen, Yu Wen Guo, Yi Wen Pan, Yi Chun Lin

^*Corresponding author for this work

Department of Chemistry

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Abstract

Reactions of [Et₄N]₂[Te(Cr(CO)₅} _n] (n = 2, 3) with a series of organic and inorganic electrophiles have been systematically studied and compared. When [Et₄N] ₂[Te{Cr(CO)₅)₂] was protonated with ~1.0 equiv of HBF₄ in MeCN, the monohydrido Te-Cr complex [Et ₄N][HTe{Cr(CO)₅)₂] ([Et₄N][1]) was obtained. However, similar protonation of [Et₄N] ₂[Te{Cr(CO)₅}₃] led to the formation of the decomposition product [Et₄N]₂[Te₂(Cr(CO) ₅}₄]. While methylation of [Et₄N] ₂[Te{Cr(CO)₅}₂] with CF₃SO ₃Me formed mono- and dimethylated products [Et₄N] [MeTe{Cr(CO)₅}₂] and Me₂Te{Cr(CO) ₅}₂ (2) stepwise, a similar reaction with [Et ₄N]₂[Te{Cr(CO)₅}₃] produced the monomethylated product [Et₄N][MeTe{Cr(CO)₅}3] (3). Further, when [Et₄N]₂[Te{Cr(CO)₅}_n] (n = 2, 3) was stirred in CH₂Cl₂ at 0°C, the Cl-functionalized products [Et₄N][ClH₂CTe{Cr(CO) ₅}_n] (n = 2, [Et₄N][4]; n = 3, [Et ₄N][5]) were produced, respectively. Similar reactions with CH ₂Cl₂ at room temperature produced corresponding CH ₂-bridged dimeric products [Et₄N]₂[CH ₂Te₂{Cr(CO)₅}_n] (n = 4; 6, [Et ₄N]₂[6]). If the bisbenzyl-containing reagent ClH ₂C(C₆H₄)₂-CH₂Cl reacted with [Et₄N]₂[Te{Cr(CO)₅}_n] (n = 2, 3), the corresponding CH₂(C₆H₄) ₂CH₂-bridged dimeric complexes [Et₄N] ₂[H₂C(C₆H₄)₂CH ₂Te₂{Cr(CO)₅}_n] (n = 4, [Et ₄N]₂[7]; n = 6, [Et₄N]₂[8]) were produced. [Et₄N]₂[Te{Cr(CO)₅}_n] (n = 2, 3) could further react with HgCl₂ in THF to give corresponding Hg-bridged products [Et₄N]₂[HgTe₂{Cr(CO) ₅)_n] (n = 4, [Et₄N]₂[9]; n = 6, [Et₄N]₂[10]). Complex 9 was found to transform to complex 10 upon its reaction with HgCl₂ in THF. Interestingly, the novel O₂-activation product [Et₄N][OTe{Cr(CO)₅} ₂] ([Et₄N][11]) was observed when [Et₄N] ₂[Te{Cr(CO)₅}₂] was bubbled with O₂ in MeCN. Complexes 1-11 were fully characterized by elemental analysis, spectroscopic methods, and/or single-crystal X-ray analysis. The nature of [Te{Cr(CO)₅}_n]^2- (n = 2, 3) and the resultant complexes were further investigated by molecular orbital calculations at the B 3LYP level of the density functional theory.

Original language	English
Pages (from-to)	6184-6196
Number of pages	13
Journal	Organometallics
Volume	26
Issue number	25
DOIs	https://doi.org/10.1021/om700789a
Publication status	Published - 2007 Dec 3

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om700789a

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@article{31c2852e1b7e4bea9c94a5a93e5a24b0,

title = "Reaction of [Et4N]2[TeCr(CO)5} n] (n = 2, 3) toward electrophiles: Reactivity comparison and theoretical calculations",

abstract = "Reactions of [Et4N]2[Te(Cr(CO)5} n] (n = 2, 3) with a series of organic and inorganic electrophiles have been systematically studied and compared. When [Et4N] 2[Te{Cr(CO)5)2] was protonated with ~1.0 equiv of HBF4 in MeCN, the monohydrido Te-Cr complex [Et 4N][HTe{Cr(CO)5)2] ([Et4N][1]) was obtained. However, similar protonation of [Et4N] 2[Te{Cr(CO)5}3] led to the formation of the decomposition product [Et4N]2[Te2(Cr(CO) 5}4]. While methylation of [Et4N] 2[Te{Cr(CO)5}2] with CF3SO 3Me formed mono- and dimethylated products [Et4N] [MeTe{Cr(CO)5}2] and Me2Te{Cr(CO) 5}2 (2) stepwise, a similar reaction with [Et 4N]2[Te{Cr(CO)5}3] produced the monomethylated product [Et4N][MeTe{Cr(CO)5}3] (3). Further, when [Et4N]2[Te{Cr(CO)5}n] (n = 2, 3) was stirred in CH2Cl2 at 0°C, the Cl-functionalized products [Et4N][ClH2CTe{Cr(CO) 5}n] (n = 2, [Et4N][4]; n = 3, [Et 4N][5]) were produced, respectively. Similar reactions with CH 2Cl2 at room temperature produced corresponding CH 2-bridged dimeric products [Et4N]2[CH 2Te2{Cr(CO)5}n] (n = 4; 6, [Et 4N]2[6]). If the bisbenzyl-containing reagent ClH 2C(C6H4)2-CH2Cl reacted with [Et4N]2[Te{Cr(CO)5}n] (n = 2, 3), the corresponding CH2(C6H4) 2CH2-bridged dimeric complexes [Et4N] 2[H2C(C6H4)2CH 2Te2{Cr(CO)5}n] (n = 4, [Et 4N]2[7]; n = 6, [Et4N]2[8]) were produced. [Et4N]2[Te{Cr(CO)5}n] (n = 2, 3) could further react with HgCl2 in THF to give corresponding Hg-bridged products [Et4N]2[HgTe2{Cr(CO) 5)n] (n = 4, [Et4N]2[9]; n = 6, [Et4N]2[10]). Complex 9 was found to transform to complex 10 upon its reaction with HgCl2 in THF. Interestingly, the novel O2-activation product [Et4N][OTe{Cr(CO)5} 2] ([Et4N][11]) was observed when [Et4N] 2[Te{Cr(CO)5}2] was bubbled with O2 in MeCN. Complexes 1-11 were fully characterized by elemental analysis, spectroscopic methods, and/or single-crystal X-ray analysis. The nature of [Te{Cr(CO)5}n]2- (n = 2, 3) and the resultant complexes were further investigated by molecular orbital calculations at the B 3LYP level of the density functional theory.",

author = "Minghuey Shieh and Ho, {Li Fang} and Chen, {Pei Chi} and Hsu, {Miao Hsing} and Chen, {Hui Lung} and Guo, {Yu Wen} and Pan, {Yi Wen} and Lin, {Yi Chun}",

year = "2007",

month = dec,

day = "3",

doi = "10.1021/om700789a",

language = "English",

volume = "26",

pages = "6184--6196",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "25",

}

TY - JOUR

T1 - Reaction of [Et4N]2[TeCr(CO)5} n] (n = 2, 3) toward electrophiles

T2 - Reactivity comparison and theoretical calculations

AU - Shieh, Minghuey

AU - Ho, Li Fang

AU - Chen, Pei Chi

AU - Hsu, Miao Hsing

AU - Chen, Hui Lung

AU - Guo, Yu Wen

AU - Pan, Yi Wen

AU - Lin, Yi Chun

PY - 2007/12/3

Y1 - 2007/12/3

N2 - Reactions of [Et4N]2[Te(Cr(CO)5} n] (n = 2, 3) with a series of organic and inorganic electrophiles have been systematically studied and compared. When [Et4N] 2[Te{Cr(CO)5)2] was protonated with ~1.0 equiv of HBF4 in MeCN, the monohydrido Te-Cr complex [Et 4N][HTe{Cr(CO)5)2] ([Et4N][1]) was obtained. However, similar protonation of [Et4N] 2[Te{Cr(CO)5}3] led to the formation of the decomposition product [Et4N]2[Te2(Cr(CO) 5}4]. While methylation of [Et4N] 2[Te{Cr(CO)5}2] with CF3SO 3Me formed mono- and dimethylated products [Et4N] [MeTe{Cr(CO)5}2] and Me2Te{Cr(CO) 5}2 (2) stepwise, a similar reaction with [Et 4N]2[Te{Cr(CO)5}3] produced the monomethylated product [Et4N][MeTe{Cr(CO)5}3] (3). Further, when [Et4N]2[Te{Cr(CO)5}n] (n = 2, 3) was stirred in CH2Cl2 at 0°C, the Cl-functionalized products [Et4N][ClH2CTe{Cr(CO) 5}n] (n = 2, [Et4N][4]; n = 3, [Et 4N][5]) were produced, respectively. Similar reactions with CH 2Cl2 at room temperature produced corresponding CH 2-bridged dimeric products [Et4N]2[CH 2Te2{Cr(CO)5}n] (n = 4; 6, [Et 4N]2[6]). If the bisbenzyl-containing reagent ClH 2C(C6H4)2-CH2Cl reacted with [Et4N]2[Te{Cr(CO)5}n] (n = 2, 3), the corresponding CH2(C6H4) 2CH2-bridged dimeric complexes [Et4N] 2[H2C(C6H4)2CH 2Te2{Cr(CO)5}n] (n = 4, [Et 4N]2[7]; n = 6, [Et4N]2[8]) were produced. [Et4N]2[Te{Cr(CO)5}n] (n = 2, 3) could further react with HgCl2 in THF to give corresponding Hg-bridged products [Et4N]2[HgTe2{Cr(CO) 5)n] (n = 4, [Et4N]2[9]; n = 6, [Et4N]2[10]). Complex 9 was found to transform to complex 10 upon its reaction with HgCl2 in THF. Interestingly, the novel O2-activation product [Et4N][OTe{Cr(CO)5} 2] ([Et4N][11]) was observed when [Et4N] 2[Te{Cr(CO)5}2] was bubbled with O2 in MeCN. Complexes 1-11 were fully characterized by elemental analysis, spectroscopic methods, and/or single-crystal X-ray analysis. The nature of [Te{Cr(CO)5}n]2- (n = 2, 3) and the resultant complexes were further investigated by molecular orbital calculations at the B 3LYP level of the density functional theory.

AB - Reactions of [Et4N]2[Te(Cr(CO)5} n] (n = 2, 3) with a series of organic and inorganic electrophiles have been systematically studied and compared. When [Et4N] 2[Te{Cr(CO)5)2] was protonated with ~1.0 equiv of HBF4 in MeCN, the monohydrido Te-Cr complex [Et 4N][HTe{Cr(CO)5)2] ([Et4N][1]) was obtained. However, similar protonation of [Et4N] 2[Te{Cr(CO)5}3] led to the formation of the decomposition product [Et4N]2[Te2(Cr(CO) 5}4]. While methylation of [Et4N] 2[Te{Cr(CO)5}2] with CF3SO 3Me formed mono- and dimethylated products [Et4N] [MeTe{Cr(CO)5}2] and Me2Te{Cr(CO) 5}2 (2) stepwise, a similar reaction with [Et 4N]2[Te{Cr(CO)5}3] produced the monomethylated product [Et4N][MeTe{Cr(CO)5}3] (3). Further, when [Et4N]2[Te{Cr(CO)5}n] (n = 2, 3) was stirred in CH2Cl2 at 0°C, the Cl-functionalized products [Et4N][ClH2CTe{Cr(CO) 5}n] (n = 2, [Et4N][4]; n = 3, [Et 4N][5]) were produced, respectively. Similar reactions with CH 2Cl2 at room temperature produced corresponding CH 2-bridged dimeric products [Et4N]2[CH 2Te2{Cr(CO)5}n] (n = 4; 6, [Et 4N]2[6]). If the bisbenzyl-containing reagent ClH 2C(C6H4)2-CH2Cl reacted with [Et4N]2[Te{Cr(CO)5}n] (n = 2, 3), the corresponding CH2(C6H4) 2CH2-bridged dimeric complexes [Et4N] 2[H2C(C6H4)2CH 2Te2{Cr(CO)5}n] (n = 4, [Et 4N]2[7]; n = 6, [Et4N]2[8]) were produced. [Et4N]2[Te{Cr(CO)5}n] (n = 2, 3) could further react with HgCl2 in THF to give corresponding Hg-bridged products [Et4N]2[HgTe2{Cr(CO) 5)n] (n = 4, [Et4N]2[9]; n = 6, [Et4N]2[10]). Complex 9 was found to transform to complex 10 upon its reaction with HgCl2 in THF. Interestingly, the novel O2-activation product [Et4N][OTe{Cr(CO)5} 2] ([Et4N][11]) was observed when [Et4N] 2[Te{Cr(CO)5}2] was bubbled with O2 in MeCN. Complexes 1-11 were fully characterized by elemental analysis, spectroscopic methods, and/or single-crystal X-ray analysis. The nature of [Te{Cr(CO)5}n]2- (n = 2, 3) and the resultant complexes were further investigated by molecular orbital calculations at the B 3LYP level of the density functional theory.

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Reaction of [Et₄N]₂[TeCr(CO)₅} _n] (n = 2, 3) toward electrophiles: Reactivity comparison and theoretical calculations

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Reaction of [Et4N]2[TeCr(CO)5} n] (n = 2, 3) toward electrophiles: Reactivity comparison and theoretical calculations

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CCDC 673753: Experimental Crystal Structure Determination

CCDC 673752: Experimental Crystal Structure Determination

CCDC 673748: Experimental Crystal Structure Determination

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Reaction of [Et₄N]₂[TeCr(CO)₅} _n] (n = 2, 3) toward electrophiles: Reactivity comparison and theoretical calculations