Isolable cyclic radical cations of heavy main-group elements

Haiyan Cui; Dengmengfei Xiao; Li Zhang; Huapeng Ruan; Yong Fang; Yue Zhao; Gengwen Tan; Lili Zhao; Gernot Frenking; Matthias Driess; Xinping Wang

doi:10.1039/c9cc09582a

Isolable cyclic radical cations of heavy main-group elements

Haiyan Cui, Dengmengfei Xiao, Li Zhang, Huapeng Ruan, Yong Fang, Yue Zhao, Gengwen Tan, Lili Zhao, Gernot Frenking, Matthias Driess, Xinping Wang

School of Chemistry and Moleculai Engineering

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

24 Scopus citations

Abstract

One-electron oxidation of 1,3-digerma-2,4-dipnictacyclobutadiene [L^HGeE]₂ (L^H = CH[CHNDipp]₂, dipp = 2,6-ⁱPr₂C₆H₃; 1: E = P; 2: E = As) with Ag[Al(OR_F)₄] (R_F = C(CF₃)₃) afforded the stable radical cation salts 1⁺·[Al(OR_F)₄]^- and 2⁺·[Al(OR_F)₄]^-, respectively. The radical cation salts have been fully characterized, in conjunction with theoretical calculations. The EPR spectroscopic studies and DFT calculations reveal that the spin density mainly resides at the heavy pnictogen atoms, rather than delocalizes over the Ge₂E₂ ring. They represent the first structurally characterized cyclic radical species composed of both heavy group 14 and 15 elements.

Original language	English
Pages (from-to)	2167-2170
Number of pages	4
Journal	Chemical Communications
Volume	56
Issue number	14
DOIs	https://doi.org/10.1039/c9cc09582a
State	Published - 18 Feb 2020

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@article{d8962822a41f4c8aa64bc1e374fa8cf9,

title = "Isolable cyclic radical cations of heavy main-group elements",

abstract = "One-electron oxidation of 1,3-digerma-2,4-dipnictacyclobutadiene [LHGeE]2 (LH = CH[CHNDipp]2, dipp = 2,6-iPr2C6H3; 1: E = P; 2: E = As) with Ag[Al(ORF)4] (RF = C(CF3)3) afforded the stable radical cation salts 1+·[Al(ORF)4]- and 2+·[Al(ORF)4]-, respectively. The radical cation salts have been fully characterized, in conjunction with theoretical calculations. The EPR spectroscopic studies and DFT calculations reveal that the spin density mainly resides at the heavy pnictogen atoms, rather than delocalizes over the Ge2E2 ring. They represent the first structurally characterized cyclic radical species composed of both heavy group 14 and 15 elements.",

author = "Haiyan Cui and Dengmengfei Xiao and Li Zhang and Huapeng Ruan and Yong Fang and Yue Zhao and Gengwen Tan and Lili Zhao and Gernot Frenking and Matthias Driess and Xinping Wang",

note = "Publisher Copyright: This journal is {\textcopyright} The Royal Society of Chemistry.",

year = "2020",

month = feb,

day = "18",

doi = "10.1039/c9cc09582a",

language = "英语",

volume = "56",

pages = "2167--2170",

journal = "Chemical Communications",

issn = "1359-7345",

publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Isolable cyclic radical cations of heavy main-group elements

AU - Cui, Haiyan

AU - Xiao, Dengmengfei

AU - Zhang, Li

AU - Ruan, Huapeng

AU - Fang, Yong

AU - Zhao, Yue

AU - Tan, Gengwen

AU - Zhao, Lili

AU - Frenking, Gernot

AU - Driess, Matthias

AU - Wang, Xinping

PY - 2020/2/18

Y1 - 2020/2/18

N2 - One-electron oxidation of 1,3-digerma-2,4-dipnictacyclobutadiene [LHGeE]2 (LH = CH[CHNDipp]2, dipp = 2,6-iPr2C6H3; 1: E = P; 2: E = As) with Ag[Al(ORF)4] (RF = C(CF3)3) afforded the stable radical cation salts 1+·[Al(ORF)4]- and 2+·[Al(ORF)4]-, respectively. The radical cation salts have been fully characterized, in conjunction with theoretical calculations. The EPR spectroscopic studies and DFT calculations reveal that the spin density mainly resides at the heavy pnictogen atoms, rather than delocalizes over the Ge2E2 ring. They represent the first structurally characterized cyclic radical species composed of both heavy group 14 and 15 elements.

AB - One-electron oxidation of 1,3-digerma-2,4-dipnictacyclobutadiene [LHGeE]2 (LH = CH[CHNDipp]2, dipp = 2,6-iPr2C6H3; 1: E = P; 2: E = As) with Ag[Al(ORF)4] (RF = C(CF3)3) afforded the stable radical cation salts 1+·[Al(ORF)4]- and 2+·[Al(ORF)4]-, respectively. The radical cation salts have been fully characterized, in conjunction with theoretical calculations. The EPR spectroscopic studies and DFT calculations reveal that the spin density mainly resides at the heavy pnictogen atoms, rather than delocalizes over the Ge2E2 ring. They represent the first structurally characterized cyclic radical species composed of both heavy group 14 and 15 elements.

UR - http://www.scopus.com/inward/record.url?scp=85079586289&partnerID=8YFLogxK

U2 - 10.1039/c9cc09582a

DO - 10.1039/c9cc09582a

M3 - 文章

C2 - 31970366

AN - SCOPUS:85079586289

SN - 1359-7345

VL - 56

SP - 2167

EP - 2170

JO - Chemical Communications

JF - Chemical Communications

IS - 14

ER -

Isolable cyclic radical cations of heavy main-group elements

Abstract

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