Trigonal-bipyramidal and square-pyramidal chromium-manganese chalcogenide clusters, [E2CrMn2(CO)n]2- (E=S, Se, Te; N=9, 10): Synthesis, electrochemistry, UV/Vis absorption, and computational studies

Minghuey Shieh, Chun Hsien Yu, Yen Yi Chu, Yu Wen Guo, Chung Yi Huang, Kai Jieah Hsing, Pei Chi Chen, Chung Feng Lee

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The reactions of E powder (E=S, Se) with a mixture of Cr(CO)6 and Mn2(CO)10 in concentrated solutions of KOH/MeOH produced two new mixed Cr-Mn-carbonyl clusters, [E2CrMn 2(CO)9]2- (E=S,; Se,). Clusters and were isostructural with one another and each displayed a trigonal-bipyramidal structure, with the CrMn2 triangle axially capped by two μ3-E atoms. The analogous telluride cluster, [Te 2CrMn2(CO)9]2- (), was obtained from the ring-closure of Te2Mn2 ring complex [Te 2Mn2Cr2(CO)18]2- (). Upon bubbling with CO, clusters and were readily converted into square-pyramidal clusters, [E2CrMn2(CO)10]2- (E=Se,; Te,), accompanied with the cleavage of one Cr-Mn bond. According to SQUID analysis, cluster was paramagnetic, with S=1 at room temperature; however, the Se analogue () was spectroscopically proposed to be diamagnetic, as verified by TD-DFT calculations. Cluster could be further carbonylated, with cleavage of the Mn-Mn bond to produce a new arachno-cluster, [Te2CrMn 2(CO)11]2- (). The formation and structural isomers, as well as electrochemistry and UV/Vis absorption, of these clusters were also elucidated by DFT calculations. Show and tellurium: Cr-Mn trigonal-bipyramidal clusters, [E2CrMn2(CO) 9]2- (E=S, Se, Te), their carbonylated square-pyramidal (SP) clusters, [E2CrMn2(CO)10]2- (E=Se, Te), and an arachno-cluster, [Te2CrMn2(CO) 11]2-, are reported. The Te SP cluster was an electron-precise paramagnetic species, whilst the Se analogue diamagnetic. DFT calculations were performed to elucidate their formation, electrochemistry, and UV/Vis absorption.

Original languageEnglish
Pages (from-to)963-973
Number of pages11
JournalChemistry - An Asian Journal
Volume8
Issue number5
DOIs
Publication statusPublished - 2013 May 1

Fingerprint

Electrochemistry
Chromium
Carbon Monoxide
Manganese
Discrete Fourier transforms
Tellurium
SQUIDs
Cluster analysis
Isomers
Powders
Cluster Analysis
Electrons

Keywords

  • chalcogens
  • chromium
  • cluster compounds
  • magnetic properties
  • manganese

ASJC Scopus subject areas

  • Chemistry(all)
  • Biochemistry
  • Organic Chemistry

Cite this

Trigonal-bipyramidal and square-pyramidal chromium-manganese chalcogenide clusters, [E2CrMn2(CO)n]2- (E=S, Se, Te; N=9, 10) : Synthesis, electrochemistry, UV/Vis absorption, and computational studies. / Shieh, Minghuey; Yu, Chun Hsien; Chu, Yen Yi; Guo, Yu Wen; Huang, Chung Yi; Hsing, Kai Jieah; Chen, Pei Chi; Lee, Chung Feng.

In: Chemistry - An Asian Journal, Vol. 8, No. 5, 01.05.2013, p. 963-973.

Research output: Contribution to journalArticle

Shieh, Minghuey ; Yu, Chun Hsien ; Chu, Yen Yi ; Guo, Yu Wen ; Huang, Chung Yi ; Hsing, Kai Jieah ; Chen, Pei Chi ; Lee, Chung Feng. / Trigonal-bipyramidal and square-pyramidal chromium-manganese chalcogenide clusters, [E2CrMn2(CO)n]2- (E=S, Se, Te; N=9, 10) : Synthesis, electrochemistry, UV/Vis absorption, and computational studies. In: Chemistry - An Asian Journal. 2013 ; Vol. 8, No. 5. pp. 963-973.
@article{7beddcdb68b940cab9b083ad67457cf1,
title = "Trigonal-bipyramidal and square-pyramidal chromium-manganese chalcogenide clusters, [E2CrMn2(CO)n]2- (E=S, Se, Te; N=9, 10): Synthesis, electrochemistry, UV/Vis absorption, and computational studies",
abstract = "The reactions of E powder (E=S, Se) with a mixture of Cr(CO)6 and Mn2(CO)10 in concentrated solutions of KOH/MeOH produced two new mixed Cr-Mn-carbonyl clusters, [E2CrMn 2(CO)9]2- (E=S,; Se,). Clusters and were isostructural with one another and each displayed a trigonal-bipyramidal structure, with the CrMn2 triangle axially capped by two μ3-E atoms. The analogous telluride cluster, [Te 2CrMn2(CO)9]2- (), was obtained from the ring-closure of Te2Mn2 ring complex [Te 2Mn2Cr2(CO)18]2- (). Upon bubbling with CO, clusters and were readily converted into square-pyramidal clusters, [E2CrMn2(CO)10]2- (E=Se,; Te,), accompanied with the cleavage of one Cr-Mn bond. According to SQUID analysis, cluster was paramagnetic, with S=1 at room temperature; however, the Se analogue () was spectroscopically proposed to be diamagnetic, as verified by TD-DFT calculations. Cluster could be further carbonylated, with cleavage of the Mn-Mn bond to produce a new arachno-cluster, [Te2CrMn 2(CO)11]2- (). The formation and structural isomers, as well as electrochemistry and UV/Vis absorption, of these clusters were also elucidated by DFT calculations. Show and tellurium: Cr-Mn trigonal-bipyramidal clusters, [E2CrMn2(CO) 9]2- (E=S, Se, Te), their carbonylated square-pyramidal (SP) clusters, [E2CrMn2(CO)10]2- (E=Se, Te), and an arachno-cluster, [Te2CrMn2(CO) 11]2-, are reported. The Te SP cluster was an electron-precise paramagnetic species, whilst the Se analogue diamagnetic. DFT calculations were performed to elucidate their formation, electrochemistry, and UV/Vis absorption.",
keywords = "chalcogens, chromium, cluster compounds, magnetic properties, manganese",
author = "Minghuey Shieh and Yu, {Chun Hsien} and Chu, {Yen Yi} and Guo, {Yu Wen} and Huang, {Chung Yi} and Hsing, {Kai Jieah} and Chen, {Pei Chi} and Lee, {Chung Feng}",
year = "2013",
month = "5",
day = "1",
doi = "10.1002/asia.201201163",
language = "English",
volume = "8",
pages = "963--973",
journal = "Chemistry - An Asian Journal",
issn = "1861-4728",
publisher = "John Wiley and Sons Ltd",
number = "5",

}

TY - JOUR

T1 - Trigonal-bipyramidal and square-pyramidal chromium-manganese chalcogenide clusters, [E2CrMn2(CO)n]2- (E=S, Se, Te; N=9, 10)

T2 - Synthesis, electrochemistry, UV/Vis absorption, and computational studies

AU - Shieh, Minghuey

AU - Yu, Chun Hsien

AU - Chu, Yen Yi

AU - Guo, Yu Wen

AU - Huang, Chung Yi

AU - Hsing, Kai Jieah

AU - Chen, Pei Chi

AU - Lee, Chung Feng

PY - 2013/5/1

Y1 - 2013/5/1

N2 - The reactions of E powder (E=S, Se) with a mixture of Cr(CO)6 and Mn2(CO)10 in concentrated solutions of KOH/MeOH produced two new mixed Cr-Mn-carbonyl clusters, [E2CrMn 2(CO)9]2- (E=S,; Se,). Clusters and were isostructural with one another and each displayed a trigonal-bipyramidal structure, with the CrMn2 triangle axially capped by two μ3-E atoms. The analogous telluride cluster, [Te 2CrMn2(CO)9]2- (), was obtained from the ring-closure of Te2Mn2 ring complex [Te 2Mn2Cr2(CO)18]2- (). Upon bubbling with CO, clusters and were readily converted into square-pyramidal clusters, [E2CrMn2(CO)10]2- (E=Se,; Te,), accompanied with the cleavage of one Cr-Mn bond. According to SQUID analysis, cluster was paramagnetic, with S=1 at room temperature; however, the Se analogue () was spectroscopically proposed to be diamagnetic, as verified by TD-DFT calculations. Cluster could be further carbonylated, with cleavage of the Mn-Mn bond to produce a new arachno-cluster, [Te2CrMn 2(CO)11]2- (). The formation and structural isomers, as well as electrochemistry and UV/Vis absorption, of these clusters were also elucidated by DFT calculations. Show and tellurium: Cr-Mn trigonal-bipyramidal clusters, [E2CrMn2(CO) 9]2- (E=S, Se, Te), their carbonylated square-pyramidal (SP) clusters, [E2CrMn2(CO)10]2- (E=Se, Te), and an arachno-cluster, [Te2CrMn2(CO) 11]2-, are reported. The Te SP cluster was an electron-precise paramagnetic species, whilst the Se analogue diamagnetic. DFT calculations were performed to elucidate their formation, electrochemistry, and UV/Vis absorption.

AB - The reactions of E powder (E=S, Se) with a mixture of Cr(CO)6 and Mn2(CO)10 in concentrated solutions of KOH/MeOH produced two new mixed Cr-Mn-carbonyl clusters, [E2CrMn 2(CO)9]2- (E=S,; Se,). Clusters and were isostructural with one another and each displayed a trigonal-bipyramidal structure, with the CrMn2 triangle axially capped by two μ3-E atoms. The analogous telluride cluster, [Te 2CrMn2(CO)9]2- (), was obtained from the ring-closure of Te2Mn2 ring complex [Te 2Mn2Cr2(CO)18]2- (). Upon bubbling with CO, clusters and were readily converted into square-pyramidal clusters, [E2CrMn2(CO)10]2- (E=Se,; Te,), accompanied with the cleavage of one Cr-Mn bond. According to SQUID analysis, cluster was paramagnetic, with S=1 at room temperature; however, the Se analogue () was spectroscopically proposed to be diamagnetic, as verified by TD-DFT calculations. Cluster could be further carbonylated, with cleavage of the Mn-Mn bond to produce a new arachno-cluster, [Te2CrMn 2(CO)11]2- (). The formation and structural isomers, as well as electrochemistry and UV/Vis absorption, of these clusters were also elucidated by DFT calculations. Show and tellurium: Cr-Mn trigonal-bipyramidal clusters, [E2CrMn2(CO) 9]2- (E=S, Se, Te), their carbonylated square-pyramidal (SP) clusters, [E2CrMn2(CO)10]2- (E=Se, Te), and an arachno-cluster, [Te2CrMn2(CO) 11]2-, are reported. The Te SP cluster was an electron-precise paramagnetic species, whilst the Se analogue diamagnetic. DFT calculations were performed to elucidate their formation, electrochemistry, and UV/Vis absorption.

KW - chalcogens

KW - chromium

KW - cluster compounds

KW - magnetic properties

KW - manganese

UR - http://www.scopus.com/inward/record.url?scp=84876940779&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84876940779&partnerID=8YFLogxK

U2 - 10.1002/asia.201201163

DO - 10.1002/asia.201201163

M3 - Article

C2 - 23610078

AN - SCOPUS:84876940779

VL - 8

SP - 963

EP - 973

JO - Chemistry - An Asian Journal

JF - Chemistry - An Asian Journal

SN - 1861-4728

IS - 5

ER -