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

Department of Chemistry

Research output: Contribution to journal › Article

13 Citations (Scopus)

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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Shieh, M., Ho, L. F., Chen, P. C., Hsu, M. H., Chen, H. L., Guo, Y. W., Pan, Y. W., & Lin, Y. C. (2007). Reaction of [Et₄N]₂[TeCr(CO)₅} _n] (n = 2, 3) toward electrophiles: Reactivity comparison and theoretical calculations. Organometallics, 26(25), 6184-6196. https://doi.org/10.1021/om700789a

@article{07abda992f434d1aa3573798857f6544,

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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