View in EDS

Photolytic Ring Expansion of Phenylphosphinidene and Its Hydrogen‐Bonded Complexes.

Saved in:
Bibliographic Details
Title: Photolytic Ring Expansion of Phenylphosphinidene and Its Hydrogen‐Bonded Complexes.
Authors: Zhan, Zhile1 (AUTHOR), Jiang, Junjie1 (AUTHOR), Wang, Lina1 (AUTHOR), Francisco, Joseph S.2 (AUTHOR) frjoseph@sas.upenn.edu, Zeng, Xiaoqing1 (AUTHOR) xqzeng@fudan.edu.cn
Source: Journal of Computational Chemistry. 1/5/2026, Vol. 47 Issue 1, p1-8. 8p.
Subjects: Phosphinidenes, Matrix isolation spectroscopy, Hydrogen bonding interactions, Cycloalkanes, Photoexcitation, Computational chemistry, Dehydrogenation
Abstract: The ring‐expansion of the parent phenylphosphinidene (2) to 1‐phospha‐1,2,4,6‐cycloheptatetraene (3) has been theoretically predicted; however, this isomer remains yet unobserved in previous experimental studies. Herein, we report the observation of 2 and 3 during photolytic (193 nm) dehydrogenation of phenylphosphine (1) in an Ar‐matrix at 10 K. Upon subsequent photoexcitation at 365 nm, 3 prefers association with molecular hydrogen in the cryogenic matrix by reformation of 1; whereas, no interconversion between 3 and 2 could be observed under the irradiation conditions. When using phenylphosphine chloride (4) as the precursor, the 1:1 complex of 2 with HCl (2–HCl) stabilized by intramolecular ClH•••π hydrogen bond is generated in the matrix, and it undergoes photo‐induced phosphinidene insertion into HCl by reformation of 4 upon photoexcitation at 365 nm. By photolyzing the matrix‐isolated complex of 1 with molecular chlorine (1–Cl2) at 310 nm, the 1:2 hydrogen‐bonded complexes of 2 with HCl are efficiently generated. Further photoexcitation of 2–2HCl at 193 nm causes ring expansion in yielding of 3–2HCl, and the reverse ring contraction from 3–2HCl to 2–2HCl occurs upon subsequent photoexcitation at 365 nm. The identification of 3 and the hydrogen‐bonded complexes 2–HCl, 2–2HCl, and 3–2HCl with matrix‐isolation IR and UV–vis spectroscopy is supported by quantum chemical calculations at the B3LYP‐D3/6‐311++G(3df,3pd) level of theory. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Computational Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
FullText Text:
  Availability: 0
Header DbId: egs
DbLabel: Engineering Source
An: 190666436
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
IllustrationInfo
Items – Name: Title
  Label: Title
  Group: Ti
  Data: Photolytic Ring Expansion of Phenylphosphinidene and Its Hydrogen‐Bonded Complexes.
– Name: Author
  Label: Authors
  Group: Au
  Data: <searchLink fieldCode="AR" term="%22Zhan%2C+Zhile%22">Zhan, Zhile</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Jiang%2C+Junjie%22">Jiang, Junjie</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Wang%2C+Lina%22">Wang, Lina</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Francisco%2C+Joseph+S%2E%22">Francisco, Joseph S.</searchLink><relatesTo>2</relatesTo> (AUTHOR)<i> frjoseph@sas.upenn.edu</i><br /><searchLink fieldCode="AR" term="%22Zeng%2C+Xiaoqing%22">Zeng, Xiaoqing</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> xqzeng@fudan.edu.cn</i>
– Name: TitleSource
  Label: Source
  Group: Src
  Data: <searchLink fieldCode="JN" term="%22Journal+of+Computational+Chemistry%22">Journal of Computational Chemistry</searchLink>. 1/5/2026, Vol. 47 Issue 1, p1-8. 8p.
– Name: Subject
  Label: Subjects
  Group: Su
  Data: <searchLink fieldCode="DE" term="%22Phosphinidenes%22">Phosphinidenes</searchLink><br /><searchLink fieldCode="DE" term="%22Matrix+isolation+spectroscopy%22">Matrix isolation spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Hydrogen+bonding+interactions%22">Hydrogen bonding interactions</searchLink><br /><searchLink fieldCode="DE" term="%22Cycloalkanes%22">Cycloalkanes</searchLink><br /><searchLink fieldCode="DE" term="%22Photoexcitation%22">Photoexcitation</searchLink><br /><searchLink fieldCode="DE" term="%22Computational+chemistry%22">Computational chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Dehydrogenation%22">Dehydrogenation</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: The ring‐expansion of the parent phenylphosphinidene (2) to 1‐phospha‐1,2,4,6‐cycloheptatetraene (3) has been theoretically predicted; however, this isomer remains yet unobserved in previous experimental studies. Herein, we report the observation of 2 and 3 during photolytic (193 nm) dehydrogenation of phenylphosphine (1) in an Ar‐matrix at 10 K. Upon subsequent photoexcitation at 365 nm, 3 prefers association with molecular hydrogen in the cryogenic matrix by reformation of 1; whereas, no interconversion between 3 and 2 could be observed under the irradiation conditions. When using phenylphosphine chloride (4) as the precursor, the 1:1 complex of 2 with HCl (2–HCl) stabilized by intramolecular ClH•••π hydrogen bond is generated in the matrix, and it undergoes photo‐induced phosphinidene insertion into HCl by reformation of 4 upon photoexcitation at 365 nm. By photolyzing the matrix‐isolated complex of 1 with molecular chlorine (1–Cl2) at 310 nm, the 1:2 hydrogen‐bonded complexes of 2 with HCl are efficiently generated. Further photoexcitation of 2–2HCl at 193 nm causes ring expansion in yielding of 3–2HCl, and the reverse ring contraction from 3–2HCl to 2–2HCl occurs upon subsequent photoexcitation at 365 nm. The identification of 3 and the hydrogen‐bonded complexes 2–HCl, 2–2HCl, and 3–2HCl with matrix‐isolation IR and UV–vis spectroscopy is supported by quantum chemical calculations at the B3LYP‐D3/6‐311++G(3df,3pd) level of theory. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of Computational Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
PLink https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=190666436
RecordInfo BibRecord:
  BibEntity:
    Identifiers:
      – Type: doi
        Value: 10.1002/jcc.70309
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 8
        StartPage: 1
    Subjects:
      – SubjectFull: Phosphinidenes
        Type: general
      – SubjectFull: Matrix isolation spectroscopy
        Type: general
      – SubjectFull: Hydrogen bonding interactions
        Type: general
      – SubjectFull: Cycloalkanes
        Type: general
      – SubjectFull: Photoexcitation
        Type: general
      – SubjectFull: Computational chemistry
        Type: general
      – SubjectFull: Dehydrogenation
        Type: general
    Titles:
      – TitleFull: Photolytic Ring Expansion of Phenylphosphinidene and Its Hydrogen‐Bonded Complexes.
        Type: main
  BibRelationships:
    HasContributorRelationships:
      – PersonEntity:
          Name:
            NameFull: Zhan, Zhile
      – PersonEntity:
          Name:
            NameFull: Jiang, Junjie
      – PersonEntity:
          Name:
            NameFull: Wang, Lina
      – PersonEntity:
          Name:
            NameFull: Francisco, Joseph S.
      – PersonEntity:
          Name:
            NameFull: Zeng, Xiaoqing
    IsPartOfRelationships:
      – BibEntity:
          Dates:
            – D: 05
              M: 01
              Text: 1/5/2026
              Type: published
              Y: 2026
          Identifiers:
            – Type: issn-print
              Value: 01928651
          Numbering:
            – Type: volume
              Value: 47
            – Type: issue
              Value: 1
          Titles:
            – TitleFull: Journal of Computational Chemistry
              Type: main
ResultId 1