View in EDS

Bimetallic complexes that merge metallocene and pincer-metal building blocks: synthesis, stereochemistry and catalytic reactivity.

Saved in:
Bibliographic Details
Title: Bimetallic complexes that merge metallocene and pincer-metal building blocks: synthesis, stereochemistry and catalytic reactivity.
Authors: Valdés, Hugo1 (AUTHOR), Germán-Acacio, Juan M.2 (AUTHOR), van Koten, Gerard3 (AUTHOR), Morales-Morales, David4 (AUTHOR) damor@unam.mx
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 2/7/2022, Vol. 51 Issue 5, p1724-1744. 21p.
Subjects: Stereochemistry, Metallocene catalysts, Transfer hydrogenation, Catalytic activity, Catalysts, Telecommunication, Metal complexes
Abstract: This perspective is to illustrate the synthesis and applications of bimetallic complexes by merging a metallocene and a (cyclopentadienyl/aryl) pincer metal complex. Four possible ways to merge metallocene and pincer-metal motifs are reported and representative examples are discussed in more detail. These bimetallic complexes have been employed in some important catalytic reactions such as cross-coupling, transfer hydrogenation or synthesis of ammonia. The metallocene fragment may tune the electronic properties of the pincer ligand, due to its redox reversible properties. Also, the presence of two metals in a single complex allows their electronic communication, which proved beneficial for, e.g., the catalytic activity of some species. The presence of the metallocene fragment provides an excellent opportunity to develop chiral catalysts, because the metallocene merger generally renders the two faces of the pincer-metal catalytic site diastereotopic. Besides, an extra chiral functionality may be added to the bimetallic species by using pincer motifs that are planar chiral, e.g. by using the different substituents of pincer ligand "arms" or non-symmetrical arene groupings. Post-functionalization of pre-formed pincer-metal complexes, via η6-coordination with an areneophile such as [CpRu]+ and [Cp*Ru]+ presents a striking strategy to obtain diastereomeric metallocene-pincer type derivatives, that actually involve half-sandwich metallocenes. This approach offers the possibility to create diastereomerically pure derivatives by using the chiral TRISPHAT anion. The authors hope that this report of the synthetic, physico-chemical properties and remarkable catalytic activities of metallocene-based pincer-metal complexes will inspire other researchers to continue exploring this realm. [ABSTRACT FROM AUTHOR]
Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry 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: 155001293
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
IllustrationInfo
Items – Name: Title
  Label: Title
  Group: Ti
  Data: Bimetallic complexes that merge metallocene and pincer-metal building blocks: synthesis, stereochemistry and catalytic reactivity.
– Name: Author
  Label: Authors
  Group: Au
  Data: <searchLink fieldCode="AR" term="%22Valdés%2C+Hugo%22">Valdés, Hugo</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Germán-Acacio%2C+Juan+M%2E%22">Germán-Acacio, Juan M.</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22van+Koten%2C+Gerard%22">van Koten, Gerard</searchLink><relatesTo>3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Morales-Morales%2C+David%22">Morales-Morales, David</searchLink><relatesTo>4</relatesTo> (AUTHOR)<i> damor@unam.mx</i>
– Name: TitleSource
  Label: Source
  Group: Src
  Data: <searchLink fieldCode="JN" term="%22Dalton+Transactions%3A+An+International+Journal+of+Inorganic+Chemistry%22">Dalton Transactions: An International Journal of Inorganic Chemistry</searchLink>. 2/7/2022, Vol. 51 Issue 5, p1724-1744. 21p.
– Name: Subject
  Label: Subjects
  Group: Su
  Data: <searchLink fieldCode="DE" term="%22Stereochemistry%22">Stereochemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Metallocene+catalysts%22">Metallocene catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Transfer+hydrogenation%22">Transfer hydrogenation</searchLink><br /><searchLink fieldCode="DE" term="%22Catalytic+activity%22">Catalytic activity</searchLink><br /><searchLink fieldCode="DE" term="%22Catalysts%22">Catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Telecommunication%22">Telecommunication</searchLink><br /><searchLink fieldCode="DE" term="%22Metal+complexes%22">Metal complexes</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: This perspective is to illustrate the synthesis and applications of bimetallic complexes by merging a metallocene and a (cyclopentadienyl/aryl) pincer metal complex. Four possible ways to merge metallocene and pincer-metal motifs are reported and representative examples are discussed in more detail. These bimetallic complexes have been employed in some important catalytic reactions such as cross-coupling, transfer hydrogenation or synthesis of ammonia. The metallocene fragment may tune the electronic properties of the pincer ligand, due to its redox reversible properties. Also, the presence of two metals in a single complex allows their electronic communication, which proved beneficial for, e.g., the catalytic activity of some species. The presence of the metallocene fragment provides an excellent opportunity to develop chiral catalysts, because the metallocene merger generally renders the two faces of the pincer-metal catalytic site diastereotopic. Besides, an extra chiral functionality may be added to the bimetallic species by using pincer motifs that are planar chiral, e.g. by using the different substituents of pincer ligand "arms" or non-symmetrical arene groupings. Post-functionalization of pre-formed pincer-metal complexes, via η6-coordination with an areneophile such as [CpRu]+ and [Cp*Ru]+ presents a striking strategy to obtain diastereomeric metallocene-pincer type derivatives, that actually involve half-sandwich metallocenes. This approach offers the possibility to create diastereomerically pure derivatives by using the chiral TRISPHAT anion. The authors hope that this report of the synthetic, physico-chemical properties and remarkable catalytic activities of metallocene-based pincer-metal complexes will inspire other researchers to continue exploring this realm. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry 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=155001293
RecordInfo BibRecord:
  BibEntity:
    Identifiers:
      – Type: doi
        Value: 10.1039/d1dt03870b
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 21
        StartPage: 1724
    Subjects:
      – SubjectFull: Stereochemistry
        Type: general
      – SubjectFull: Metallocene catalysts
        Type: general
      – SubjectFull: Transfer hydrogenation
        Type: general
      – SubjectFull: Catalytic activity
        Type: general
      – SubjectFull: Catalysts
        Type: general
      – SubjectFull: Telecommunication
        Type: general
      – SubjectFull: Metal complexes
        Type: general
    Titles:
      – TitleFull: Bimetallic complexes that merge metallocene and pincer-metal building blocks: synthesis, stereochemistry and catalytic reactivity.
        Type: main
  BibRelationships:
    HasContributorRelationships:
      – PersonEntity:
          Name:
            NameFull: Valdés, Hugo
      – PersonEntity:
          Name:
            NameFull: Germán-Acacio, Juan M.
      – PersonEntity:
          Name:
            NameFull: van Koten, Gerard
      – PersonEntity:
          Name:
            NameFull: Morales-Morales, David
    IsPartOfRelationships:
      – BibEntity:
          Dates:
            – D: 07
              M: 02
              Text: 2/7/2022
              Type: published
              Y: 2022
          Identifiers:
            – Type: issn-print
              Value: 14779226
          Numbering:
            – Type: volume
              Value: 51
            – Type: issue
              Value: 5
          Titles:
            – TitleFull: Dalton Transactions: An International Journal of Inorganic Chemistry
              Type: main
ResultId 1