Effect of M(CO)3 (M = Cr, Mn+) on aromatic C-Cl BDE in (η6-ArCl)M(CO)3 complexes

Hechun Lin; Qian Chen; Lidong Cao; Li Yang; Yun Dong Wu; Chaozhong Li

doi:10.1021/jo060154i

Effect of M(CO)₃ (M = Cr, Mn⁺) on aromatic C-Cl BDE in (η⁶-ArCl)M(CO)₃ complexes

Hechun Lin, Qian Chen, Lidong Cao, Li Yang, Yun Dong Wu, Chaozhong Li

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19 Scopus citations

Abstract

The coordination of Cr(CO)₃ to chlorobenzenes significantly reduces the C-Cl bond dissociation energy. Treatment of chloroarene-Cr(CO) ₃ complexes with SmI₂/HMPA at room temperature led to complete dechlorination. Reaction of o-allyloxychlorobenzene-Cr(CO)₃ complexes with SmI₂ at room temperature resulted in the corresponding dechlorinative cyclization products in good to excellent yields. Competition experiments indicated the following relative reactivities of dehalogenation by SmI₂: PhI/PhCl-Cr(CO)₃/PhBr/PhCl = 50:1:0.3:<0.001. On the other hand, the coordination of Mn(CO)₃⁺ to chlorobenzene showed a much smaller activation effect. Density functional theory calculations revealed that the spin delocalization effect of the metal center plays an important role in the C-Cl bond activation.

Original language	English
Pages (from-to)	3328-3331
Number of pages	4
Journal	Journal of Organic Chemistry
Volume	71
Issue number	8
DOIs	https://doi.org/10.1021/jo060154i
State	Published - 14 Apr 2006
Externally published	Yes

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title = "Effect of M(CO)3 (M = Cr, Mn+) on aromatic C-Cl BDE in (η6-ArCl)M(CO)3 complexes",

abstract = "The coordination of Cr(CO)3 to chlorobenzenes significantly reduces the C-Cl bond dissociation energy. Treatment of chloroarene-Cr(CO) 3 complexes with SmI2/HMPA at room temperature led to complete dechlorination. Reaction of o-allyloxychlorobenzene-Cr(CO)3 complexes with SmI2 at room temperature resulted in the corresponding dechlorinative cyclization products in good to excellent yields. Competition experiments indicated the following relative reactivities of dehalogenation by SmI2: PhI/PhCl-Cr(CO)3/PhBr/PhCl = 50:1:0.3:<0.001. On the other hand, the coordination of Mn(CO)3+ to chlorobenzene showed a much smaller activation effect. Density functional theory calculations revealed that the spin delocalization effect of the metal center plays an important role in the C-Cl bond activation.",

author = "Hechun Lin and Qian Chen and Lidong Cao and Li Yang and Wu, \{Yun Dong\} and Chaozhong Li",

year = "2006",

month = apr,

day = "14",

doi = "10.1021/jo060154i",

language = "英语",

volume = "71",

pages = "3328--3331",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

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number = "8",

}

TY - JOUR

T1 - Effect of M(CO)3 (M = Cr, Mn+) on aromatic C-Cl BDE in (η6-ArCl)M(CO)3 complexes

AU - Lin, Hechun

AU - Chen, Qian

AU - Cao, Lidong

AU - Yang, Li

AU - Wu, Yun Dong

AU - Li, Chaozhong

PY - 2006/4/14

Y1 - 2006/4/14

N2 - The coordination of Cr(CO)3 to chlorobenzenes significantly reduces the C-Cl bond dissociation energy. Treatment of chloroarene-Cr(CO) 3 complexes with SmI2/HMPA at room temperature led to complete dechlorination. Reaction of o-allyloxychlorobenzene-Cr(CO)3 complexes with SmI2 at room temperature resulted in the corresponding dechlorinative cyclization products in good to excellent yields. Competition experiments indicated the following relative reactivities of dehalogenation by SmI2: PhI/PhCl-Cr(CO)3/PhBr/PhCl = 50:1:0.3:<0.001. On the other hand, the coordination of Mn(CO)3+ to chlorobenzene showed a much smaller activation effect. Density functional theory calculations revealed that the spin delocalization effect of the metal center plays an important role in the C-Cl bond activation.

AB - The coordination of Cr(CO)3 to chlorobenzenes significantly reduces the C-Cl bond dissociation energy. Treatment of chloroarene-Cr(CO) 3 complexes with SmI2/HMPA at room temperature led to complete dechlorination. Reaction of o-allyloxychlorobenzene-Cr(CO)3 complexes with SmI2 at room temperature resulted in the corresponding dechlorinative cyclization products in good to excellent yields. Competition experiments indicated the following relative reactivities of dehalogenation by SmI2: PhI/PhCl-Cr(CO)3/PhBr/PhCl = 50:1:0.3:<0.001. On the other hand, the coordination of Mn(CO)3+ to chlorobenzene showed a much smaller activation effect. Density functional theory calculations revealed that the spin delocalization effect of the metal center plays an important role in the C-Cl bond activation.

UR - https://www.scopus.com/pages/publications/33645782201

U2 - 10.1021/jo060154i

DO - 10.1021/jo060154i

M3 - 文章

AN - SCOPUS:33645782201

SN - 0022-3263

VL - 71

SP - 3328

EP - 3331

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 8

ER -

Effect of M(CO)₃ (M = Cr, Mn⁺) on aromatic C-Cl BDE in (η⁶-ArCl)M(CO)₃ complexes

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