Copper halide-lncorporated tellurium-iron carbonyl complexes: Transformation, electrochemical properties, and theoretical calculations

Bo Gaun Chen; Chia Hua Ho; Chang Ju Lee; Minghuey Shieh

doi:10.1021/ic901647n

Copper halide-lncorporated tellurium-iron carbonyl complexes: Transformation, electrochemical properties, and theoretical calculations

Bo Gaun Chen, Chia Hua Ho, Chang Ju Lee, Minghuey Shieh

Department of Chemistry

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

16 Citations (Scopus)

Abstract

When the tellurium-capped tri-iron carbonyl cluster [Et₄N] ₂[TeFe₃(CO)₉] was treated with 1 equiv of CuX In THF at O °C, CuX-incorporated clusters [Et₄N] ₂[TeFe₃(CO)₉CuX] (X= Cl, [Et₄N] ₂[1a]; Br, [Et₄N]₂[1b]; I, [Et ₄N]₂[1c]) were formed, respectively. X-ray analysis showed that 1a-1c each exhibited a TeFe3 core with one Fe-Fe bond bridged by one CuX fragment. When the reactions were carried out at a molar ratio of 1:2 (X= Cl, Br) or 1:3 (X= I) In tetrahydrofuran (THF) or MeCN at O °C, Cu ₂X₂-lncorporated clusters [Et₄N] ₂[TeFe₃(CO)₉Cu₂X₂] (X= Cl, [Et₄N]₂[2a]; Br, [Et₄N]₂[2b]; I, [Et₄N]₂[2c]) were obtained, respectively. Cluster 2a was structurally characterized by X-ray analysis to display a TeFe₃ core, In which one TeFe₂ plane was asymmetrically bridged and capped by one μ₃-CuCl and another μ₄-CuCI with two Cu atoms bonded. Complexes 1a-1c underwent skeleton expansion to form Cu ₃Xincorporated di-TeFe₃ clusters [(TeFe ₃(CO)₉}₂Cu₃X]^2- (X= Cl, 3a; Br, 3b; 1,3c), respectively, upon treatment with 1 equiv of [Cu(MeCN) ₄][BF₄] at O °C. X-ray analysis snowed that 3b and 3c each consisted of two TeFe3 clusters that were linked by a Cu₃X moiety. However, a similar reaction for 1a and 1b with 1 equiv of [Cu(MeCN) ₄][BF₄] at room temperature produced Cu₄X ₂-llnked di-TeFe3 clusters [(TeFe₃(CO)₉} ₂Cu₄X₂]^2- (X= Cl, 4a; Br, 4b). Cluster 4a was shown by X-ray analysis to have two TeFe3 cores linked by a Cu₄Cl₂ moiety. Clusters 4a and 4b were also produced directly from the reaction of [Et₄N]₂[TeFe ₃(CO)₉] with 4 equiv of CuX (X= Cl, Br) In THF. Furthermore, the nature, the formation, the cluster transformation, and the electrochemistry of the CuX-incorporated mono- or di-TeFe₃ clusters are explained in terms of the effects of tellurium, copper hallde, and the size of the metal skeleton, all of which are elucidated by molecular calculations at the B3LYP level of density functional theory.

Original language	English
Pages (from-to)	10757-10768
Number of pages	12
Journal	Inorganic Chemistry
Volume	48
Issue number	22
DOIs	https://doi.org/10.1021/ic901647n
Publication status	Published - 2009 Nov 16

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/ic901647n

Fingerprint Dive into the research topics of 'Copper halide-lncorporated tellurium-iron carbonyl complexes: Transformation, electrochemical properties, and theoretical calculations'. Together they form a unique fingerprint.

Cite this

@article{9a0218c0cd4846d6b9ab9d2368393dff,

title = "Copper halide-lncorporated tellurium-iron carbonyl complexes: Transformation, electrochemical properties, and theoretical calculations",

abstract = "When the tellurium-capped tri-iron carbonyl cluster [Et4N] 2[TeFe3(CO)9] was treated with 1 equiv of CuX In THF at O °C, CuX-incorporated clusters [Et4N] 2[TeFe3(CO)9CuX] (X= Cl, [Et4N] 2[1a]; Br, [Et4N]2[1b]; I, [Et 4N]2[1c]) were formed, respectively. X-ray analysis showed that 1a-1c each exhibited a TeFe3 core with one Fe-Fe bond bridged by one CuX fragment. When the reactions were carried out at a molar ratio of 1:2 (X= Cl, Br) or 1:3 (X= I) In tetrahydrofuran (THF) or MeCN at O °C, Cu 2X2-lncorporated clusters [Et4N] 2[TeFe3(CO)9Cu2X2] (X= Cl, [Et4N]2[2a]; Br, [Et4N]2[2b]; I, [Et4N]2[2c]) were obtained, respectively. Cluster 2a was structurally characterized by X-ray analysis to display a TeFe3 core, In which one TeFe2 plane was asymmetrically bridged and capped by one μ3-CuCl and another μ4-CuCI with two Cu atoms bonded. Complexes 1a-1c underwent skeleton expansion to form Cu 3Xincorporated di-TeFe3 clusters [(TeFe 3(CO)9}2Cu3X]2- (X= Cl, 3a; Br, 3b; 1,3c), respectively, upon treatment with 1 equiv of [Cu(MeCN) 4][BF4] at O °C. X-ray analysis snowed that 3b and 3c each consisted of two TeFe3 clusters that were linked by a Cu3X moiety. However, a similar reaction for 1a and 1b with 1 equiv of [Cu(MeCN) 4][BF4] at room temperature produced Cu4X 2-llnked di-TeFe3 clusters [(TeFe3(CO)9} 2Cu4X2]2- (X= Cl, 4a; Br, 4b). Cluster 4a was shown by X-ray analysis to have two TeFe3 cores linked by a Cu4Cl2 moiety. Clusters 4a and 4b were also produced directly from the reaction of [Et4N]2[TeFe 3(CO)9] with 4 equiv of CuX (X= Cl, Br) In THF. Furthermore, the nature, the formation, the cluster transformation, and the electrochemistry of the CuX-incorporated mono- or di-TeFe3 clusters are explained in terms of the effects of tellurium, copper hallde, and the size of the metal skeleton, all of which are elucidated by molecular calculations at the B3LYP level of density functional theory.",

author = "Chen, {Bo Gaun} and Ho, {Chia Hua} and Lee, {Chang Ju} and Minghuey Shieh",

year = "2009",

month = nov,

day = "16",

doi = "10.1021/ic901647n",

language = "English",

volume = "48",

pages = "10757--10768",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "22",

}

TY - JOUR

T1 - Copper halide-lncorporated tellurium-iron carbonyl complexes

T2 - Transformation, electrochemical properties, and theoretical calculations

AU - Chen, Bo Gaun

AU - Ho, Chia Hua

AU - Lee, Chang Ju

AU - Shieh, Minghuey

PY - 2009/11/16

Y1 - 2009/11/16

N2 - When the tellurium-capped tri-iron carbonyl cluster [Et4N] 2[TeFe3(CO)9] was treated with 1 equiv of CuX In THF at O °C, CuX-incorporated clusters [Et4N] 2[TeFe3(CO)9CuX] (X= Cl, [Et4N] 2[1a]; Br, [Et4N]2[1b]; I, [Et 4N]2[1c]) were formed, respectively. X-ray analysis showed that 1a-1c each exhibited a TeFe3 core with one Fe-Fe bond bridged by one CuX fragment. When the reactions were carried out at a molar ratio of 1:2 (X= Cl, Br) or 1:3 (X= I) In tetrahydrofuran (THF) or MeCN at O °C, Cu 2X2-lncorporated clusters [Et4N] 2[TeFe3(CO)9Cu2X2] (X= Cl, [Et4N]2[2a]; Br, [Et4N]2[2b]; I, [Et4N]2[2c]) were obtained, respectively. Cluster 2a was structurally characterized by X-ray analysis to display a TeFe3 core, In which one TeFe2 plane was asymmetrically bridged and capped by one μ3-CuCl and another μ4-CuCI with two Cu atoms bonded. Complexes 1a-1c underwent skeleton expansion to form Cu 3Xincorporated di-TeFe3 clusters [(TeFe 3(CO)9}2Cu3X]2- (X= Cl, 3a; Br, 3b; 1,3c), respectively, upon treatment with 1 equiv of [Cu(MeCN) 4][BF4] at O °C. X-ray analysis snowed that 3b and 3c each consisted of two TeFe3 clusters that were linked by a Cu3X moiety. However, a similar reaction for 1a and 1b with 1 equiv of [Cu(MeCN) 4][BF4] at room temperature produced Cu4X 2-llnked di-TeFe3 clusters [(TeFe3(CO)9} 2Cu4X2]2- (X= Cl, 4a; Br, 4b). Cluster 4a was shown by X-ray analysis to have two TeFe3 cores linked by a Cu4Cl2 moiety. Clusters 4a and 4b were also produced directly from the reaction of [Et4N]2[TeFe 3(CO)9] with 4 equiv of CuX (X= Cl, Br) In THF. Furthermore, the nature, the formation, the cluster transformation, and the electrochemistry of the CuX-incorporated mono- or di-TeFe3 clusters are explained in terms of the effects of tellurium, copper hallde, and the size of the metal skeleton, all of which are elucidated by molecular calculations at the B3LYP level of density functional theory.

AB - When the tellurium-capped tri-iron carbonyl cluster [Et4N] 2[TeFe3(CO)9] was treated with 1 equiv of CuX In THF at O °C, CuX-incorporated clusters [Et4N] 2[TeFe3(CO)9CuX] (X= Cl, [Et4N] 2[1a]; Br, [Et4N]2[1b]; I, [Et 4N]2[1c]) were formed, respectively. X-ray analysis showed that 1a-1c each exhibited a TeFe3 core with one Fe-Fe bond bridged by one CuX fragment. When the reactions were carried out at a molar ratio of 1:2 (X= Cl, Br) or 1:3 (X= I) In tetrahydrofuran (THF) or MeCN at O °C, Cu 2X2-lncorporated clusters [Et4N] 2[TeFe3(CO)9Cu2X2] (X= Cl, [Et4N]2[2a]; Br, [Et4N]2[2b]; I, [Et4N]2[2c]) were obtained, respectively. Cluster 2a was structurally characterized by X-ray analysis to display a TeFe3 core, In which one TeFe2 plane was asymmetrically bridged and capped by one μ3-CuCl and another μ4-CuCI with two Cu atoms bonded. Complexes 1a-1c underwent skeleton expansion to form Cu 3Xincorporated di-TeFe3 clusters [(TeFe 3(CO)9}2Cu3X]2- (X= Cl, 3a; Br, 3b; 1,3c), respectively, upon treatment with 1 equiv of [Cu(MeCN) 4][BF4] at O °C. X-ray analysis snowed that 3b and 3c each consisted of two TeFe3 clusters that were linked by a Cu3X moiety. However, a similar reaction for 1a and 1b with 1 equiv of [Cu(MeCN) 4][BF4] at room temperature produced Cu4X 2-llnked di-TeFe3 clusters [(TeFe3(CO)9} 2Cu4X2]2- (X= Cl, 4a; Br, 4b). Cluster 4a was shown by X-ray analysis to have two TeFe3 cores linked by a Cu4Cl2 moiety. Clusters 4a and 4b were also produced directly from the reaction of [Et4N]2[TeFe 3(CO)9] with 4 equiv of CuX (X= Cl, Br) In THF. Furthermore, the nature, the formation, the cluster transformation, and the electrochemistry of the CuX-incorporated mono- or di-TeFe3 clusters are explained in terms of the effects of tellurium, copper hallde, and the size of the metal skeleton, all of which are elucidated by molecular calculations at the B3LYP level of density functional theory.

UR - http://www.scopus.com/inward/record.url?scp=70450186704&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=70450186704&partnerID=8YFLogxK

U2 - 10.1021/ic901647n

DO - 10.1021/ic901647n

M3 - Article

C2 - 19831367

AN - SCOPUS:70450186704

VL - 48

SP - 10757

EP - 10768

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 22

ER -