Reactions of iron acyl chalcogenide clusters with electrophiles: Reactivity comparison and theoretical calculations

Minghuey Shieh; Yen Yi Chu; Hsin Hung Chi; Horng Sun Chen; Kai Jieah Hsing; Chung Yi Huang

doi:10.1002/jccs.201200553

Reactions of iron acyl chalcogenide clusters with electrophiles: Reactivity comparison and theoretical calculations

Minghuey Shieh^*, Yen Yi Chu, Hsin Hung Chi, Horng Sun Chen, Kai Jieah Hsing, Chung Yi Huang

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The reactions of two types of EFe3-based acyl clusters [EFe ₃(CO)₉C(O)C(H)CCH₂)]∼ (E = S, 1; Se, 2; Te, 3) with different electrophiles have been systematically studied and compared. When the sulfur-substituted allylcarbonyl Fe3-cluster [Fe₃(CO) ₉{|μ-η²:η¹:η³-C(O) CHC(S)CH₂}]^- (1) was treated with CH₃COCl in CH₂Cl₂, the Fischer-type acyloxy carbene cluster [Fe ₃(CO)₉{|μ₃-η²: η⁴:η¹-C(OCOCH3)-C(H)C(S)CH₂}] (4) was obtained, along with the previously reported SC(O)C(CH₃)=CH bridged Fe2-complex [Fe2(CO)6{μ-η²:η³-SC(O)C(CH3)CH}] (5) and [HSFe₃(CO)₉]^-. Similar acetylation of the allylcarbonyl SeFe₃-cluster [(μ₃-Se)Fe ₃(CO)₉(μ₃-η¹: η¹:η³- C(O)C(H)CCH₂)]^- (2) produced the Fe2-carbene complex [Fe₂(CO)₆{μ- η|²:η³-C(OCOCH₃)C(H)C(Se)CH2}] (6) and the propyne-bridged SeFe₃-complex [(μ₃-Se)Fe ₃(CO)₉{|μ-η¹:η²: η¹-C(CH₃)=C(H)}] (7) as well as [HSeFe ₃(CO)₉]^- and [Se₂Fe ₃(CO)₉]. However, when the analogous TeFe ₃-based allylcarbonyl cluster [μ3-Te)Fe₃(CO) ₉(|μ3-η¹:η¹:η³-C(O) C(H)CCH₂)]^- (3) reacted with CH₃COCl, only the fragmentation product [Te₂Fe₃(CO)₉] was formed. Further acidification of cluster 1 with HBF₄ proceeded to form complex 5 and [HSFe3(CO)9]^-. Similar acidification of 2 formed the propyne-capped complex 7, however, the protonation of 3 led to the formation of [Te₂Fe₃(CO)₉]. Contrast to the reported reactions of 1 and 3, the reaction of 2 with [Cu(CH₃CN) ₄][BF₄] formed complex 7 and a new C(O)CH=C(Se)(CH ₃) bridged Fe2-complex [Fe₂(CO)₆{μ- η|²:η³-C(O)CHC(Se)(CH₃)}] (8). The nature and formation of new carbene complexes 4 and 6 were further elucidated with the aid of molecular orbital calculations at the B3PW91 level of density functional theory.

Original language	English
Pages (from-to)	725-734
Number of pages	10
Journal	Journal of the Chinese Chemical Society
Volume	60
Issue number	7
DOIs	https://doi.org/10.1002/jccs.201200553
Publication status	Published - 2013 Jul

Keywords

Acyl
Acyloxy
Carbene
Carbonyl
Chalcogen
Cluster
Iron

ASJC Scopus subject areas

General Chemistry

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10.1002/jccs.201200553

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@article{c34e4864bb834df9a81d44f2659b8bbf,

title = "Reactions of iron acyl chalcogenide clusters with electrophiles: Reactivity comparison and theoretical calculations",

abstract = "The reactions of two types of EFe3-based acyl clusters [EFe 3(CO)9C(O)C(H)CCH2)]∼ (E = S, 1; Se, 2; Te, 3) with different electrophiles have been systematically studied and compared. When the sulfur-substituted allylcarbonyl Fe3-cluster [Fe3(CO) 9{|μ-η2:η1:η3-C(O) CHC(S)CH2}]- (1) was treated with CH3COCl in CH2Cl2, the Fischer-type acyloxy carbene cluster [Fe 3(CO)9{|μ3-η2: η4:η1-C(OCOCH3)-C(H)C(S)CH2}] (4) was obtained, along with the previously reported SC(O)C(CH3)=CH bridged Fe2-complex [Fe2(CO)6{μ-η2:η3-SC(O)C(CH3)CH}] (5) and [HSFe3(CO)9]-. Similar acetylation of the allylcarbonyl SeFe3-cluster [(μ3-Se)Fe 3(CO)9(μ3-η1: η1:η3- C(O)C(H)CCH2)]- (2) produced the Fe2-carbene complex [Fe2(CO)6{μ- η|2:η3-C(OCOCH3)C(H)C(Se)CH2}] (6) and the propyne-bridged SeFe3-complex [(μ3-Se)Fe 3(CO)9{|μ-η1:η2: η1-C(CH3)=C(H)}] (7) as well as [HSeFe 3(CO)9]- and [Se2Fe 3(CO)9]. However, when the analogous TeFe 3-based allylcarbonyl cluster [μ3-Te)Fe3(CO) 9(|μ3-η1:η1:η3-C(O) C(H)CCH2)]- (3) reacted with CH3COCl, only the fragmentation product [Te2Fe3(CO)9] was formed. Further acidification of cluster 1 with HBF4 proceeded to form complex 5 and [HSFe3(CO)9]-. Similar acidification of 2 formed the propyne-capped complex 7, however, the protonation of 3 led to the formation of [Te2Fe3(CO)9]. Contrast to the reported reactions of 1 and 3, the reaction of 2 with [Cu(CH3CN) 4][BF4] formed complex 7 and a new C(O)CH=C(Se)(CH 3) bridged Fe2-complex [Fe2(CO)6{μ- η|2:η3-C(O)CHC(Se)(CH3)}] (8). The nature and formation of new carbene complexes 4 and 6 were further elucidated with the aid of molecular orbital calculations at the B3PW91 level of density functional theory.",

keywords = "Acyl, Acyloxy, Carbene, Carbonyl, Chalcogen, Cluster, Iron",

author = "Minghuey Shieh and Chu, {Yen Yi} and Chi, {Hsin Hung} and Chen, {Horng Sun} and Hsing, {Kai Jieah} and Huang, {Chung Yi}",

year = "2013",

month = jul,

doi = "10.1002/jccs.201200553",

language = "English",

volume = "60",

pages = "725--734",

journal = "Journal of the Chinese Chemical Society",

issn = "0009-4536",

publisher = "Chinese Chemical Society",

number = "7",

}

TY - JOUR

T1 - Reactions of iron acyl chalcogenide clusters with electrophiles

T2 - Reactivity comparison and theoretical calculations

AU - Shieh, Minghuey

AU - Chu, Yen Yi

AU - Chi, Hsin Hung

AU - Chen, Horng Sun

AU - Hsing, Kai Jieah

AU - Huang, Chung Yi

PY - 2013/7

Y1 - 2013/7

N2 - The reactions of two types of EFe3-based acyl clusters [EFe 3(CO)9C(O)C(H)CCH2)]∼ (E = S, 1; Se, 2; Te, 3) with different electrophiles have been systematically studied and compared. When the sulfur-substituted allylcarbonyl Fe3-cluster [Fe3(CO) 9{|μ-η2:η1:η3-C(O) CHC(S)CH2}]- (1) was treated with CH3COCl in CH2Cl2, the Fischer-type acyloxy carbene cluster [Fe 3(CO)9{|μ3-η2: η4:η1-C(OCOCH3)-C(H)C(S)CH2}] (4) was obtained, along with the previously reported SC(O)C(CH3)=CH bridged Fe2-complex [Fe2(CO)6{μ-η2:η3-SC(O)C(CH3)CH}] (5) and [HSFe3(CO)9]-. Similar acetylation of the allylcarbonyl SeFe3-cluster [(μ3-Se)Fe 3(CO)9(μ3-η1: η1:η3- C(O)C(H)CCH2)]- (2) produced the Fe2-carbene complex [Fe2(CO)6{μ- η|2:η3-C(OCOCH3)C(H)C(Se)CH2}] (6) and the propyne-bridged SeFe3-complex [(μ3-Se)Fe 3(CO)9{|μ-η1:η2: η1-C(CH3)=C(H)}] (7) as well as [HSeFe 3(CO)9]- and [Se2Fe 3(CO)9]. However, when the analogous TeFe 3-based allylcarbonyl cluster [μ3-Te)Fe3(CO) 9(|μ3-η1:η1:η3-C(O) C(H)CCH2)]- (3) reacted with CH3COCl, only the fragmentation product [Te2Fe3(CO)9] was formed. Further acidification of cluster 1 with HBF4 proceeded to form complex 5 and [HSFe3(CO)9]-. Similar acidification of 2 formed the propyne-capped complex 7, however, the protonation of 3 led to the formation of [Te2Fe3(CO)9]. Contrast to the reported reactions of 1 and 3, the reaction of 2 with [Cu(CH3CN) 4][BF4] formed complex 7 and a new C(O)CH=C(Se)(CH 3) bridged Fe2-complex [Fe2(CO)6{μ- η|2:η3-C(O)CHC(Se)(CH3)}] (8). The nature and formation of new carbene complexes 4 and 6 were further elucidated with the aid of molecular orbital calculations at the B3PW91 level of density functional theory.

AB - The reactions of two types of EFe3-based acyl clusters [EFe 3(CO)9C(O)C(H)CCH2)]∼ (E = S, 1; Se, 2; Te, 3) with different electrophiles have been systematically studied and compared. When the sulfur-substituted allylcarbonyl Fe3-cluster [Fe3(CO) 9{|μ-η2:η1:η3-C(O) CHC(S)CH2}]- (1) was treated with CH3COCl in CH2Cl2, the Fischer-type acyloxy carbene cluster [Fe 3(CO)9{|μ3-η2: η4:η1-C(OCOCH3)-C(H)C(S)CH2}] (4) was obtained, along with the previously reported SC(O)C(CH3)=CH bridged Fe2-complex [Fe2(CO)6{μ-η2:η3-SC(O)C(CH3)CH}] (5) and [HSFe3(CO)9]-. Similar acetylation of the allylcarbonyl SeFe3-cluster [(μ3-Se)Fe 3(CO)9(μ3-η1: η1:η3- C(O)C(H)CCH2)]- (2) produced the Fe2-carbene complex [Fe2(CO)6{μ- η|2:η3-C(OCOCH3)C(H)C(Se)CH2}] (6) and the propyne-bridged SeFe3-complex [(μ3-Se)Fe 3(CO)9{|μ-η1:η2: η1-C(CH3)=C(H)}] (7) as well as [HSeFe 3(CO)9]- and [Se2Fe 3(CO)9]. However, when the analogous TeFe 3-based allylcarbonyl cluster [μ3-Te)Fe3(CO) 9(|μ3-η1:η1:η3-C(O) C(H)CCH2)]- (3) reacted with CH3COCl, only the fragmentation product [Te2Fe3(CO)9] was formed. Further acidification of cluster 1 with HBF4 proceeded to form complex 5 and [HSFe3(CO)9]-. Similar acidification of 2 formed the propyne-capped complex 7, however, the protonation of 3 led to the formation of [Te2Fe3(CO)9]. Contrast to the reported reactions of 1 and 3, the reaction of 2 with [Cu(CH3CN) 4][BF4] formed complex 7 and a new C(O)CH=C(Se)(CH 3) bridged Fe2-complex [Fe2(CO)6{μ- η|2:η3-C(O)CHC(Se)(CH3)}] (8). The nature and formation of new carbene complexes 4 and 6 were further elucidated with the aid of molecular orbital calculations at the B3PW91 level of density functional theory.

KW - Acyl

KW - Acyloxy

KW - Carbene

KW - Carbonyl

KW - Chalcogen

KW - Cluster

KW - Iron

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DO - 10.1002/jccs.201200553

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AN - SCOPUS:84885639075

SN - 0009-4536

VL - 60

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JO - Journal of the Chinese Chemical Society

JF - Journal of the Chinese Chemical Society

IS - 7

ER -

Reactions of iron acyl chalcogenide clusters with electrophiles: Reactivity comparison and theoretical calculations

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