View in EDS

Two new bulky amido ligands useful for the preparation of metal complexes and examples of their reactivity

Saved in:
Bibliographic Details
Title: Two new bulky amido ligands useful for the preparation of metal complexes and examples of their reactivity
Authors: Tang, Yongjun1, Zakharov, Lev N.2, Rheingold, Arnold L.2, Kemp, Richard A.1,3 rakemp@unm.edu
Source: Inorganica Chimica Acta. Feb2006, Vol. 359 Issue 3, p775-781. 7p.
Subjects: Ligands (Chemistry), Phenyl compounds, Amines, Crystallography
Abstract: Abstract: The search for new ligands with interesting properties is a quest that can occupy much of a synthetic chemist’s time. We have recently discovered two new ligands based on an adamantyl-substituted, 2,6- i Pr2-substituted phenyl (Dipp) system. In an attempt to prepare the extremely bulky amine [(ad)(2,6- i Pr2C6H3)NH] (ad=adamantyl) we found instead that the adamantyl group attacks the aromatic ring in the 4-position to form a new primary amine, (4-ad-2,6- i Pr2C6H2)NH2 (1) (ad-Dipp-NH2), characterized by normal techniques. Compound 1 could be converted into a Li salt by a 1:1 reaction with n BuLi, or converted into a more bulky silylamine, [(ad-Dipp)NH(SiMe3)] (3), by treatment with Me3SiCl. We have characterized the lithium salt by X-ray crystallography as the dimeric complex, [(ad-Dipp)NHLi(Et2O)]2 (2). The lithium amide can be used as a reagent towards metal halides, and we have discovered that its reaction with SnCl2 yields a compound with a tetrameric, [Sn–N]4 cubane-like cage structure. We have also demonstrated the ligand behavior of 3 by its reaction with Bu2Mg in THF to form a monomeric Mg-amide with two THF solvent molecules attached. These new ligands can provide advantages over conventional ligands in terms of improved solubility and ease of crystallization. [Copyright &y& Elsevier]
Copyright of Inorganica Chimica Acta is the property of Elsevier B.V. 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: 19468519
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
IllustrationInfo
Items – Name: Title
  Label: Title
  Group: Ti
  Data: Two new bulky amido ligands useful for the preparation of metal complexes and examples of their reactivity
– Name: Author
  Label: Authors
  Group: Au
  Data: <searchLink fieldCode="AR" term="%22Tang%2C+Yongjun%22">Tang, Yongjun</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Zakharov%2C+Lev+N%2E%22">Zakharov, Lev N.</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Rheingold%2C+Arnold+L%2E%22">Rheingold, Arnold L.</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Kemp%2C+Richard+A%2E%22">Kemp, Richard A.</searchLink><relatesTo>1,3</relatesTo><i> rakemp@unm.edu</i>
– Name: TitleSource
  Label: Source
  Group: Src
  Data: <searchLink fieldCode="JN" term="%22Inorganica+Chimica+Acta%22">Inorganica Chimica Acta</searchLink>. Feb2006, Vol. 359 Issue 3, p775-781. 7p.
– Name: Subject
  Label: Subjects
  Group: Su
  Data: <searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Phenyl+compounds%22">Phenyl compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Amines%22">Amines</searchLink><br /><searchLink fieldCode="DE" term="%22Crystallography%22">Crystallography</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: Abstract: The search for new ligands with interesting properties is a quest that can occupy much of a synthetic chemist’s time. We have recently discovered two new ligands based on an adamantyl-substituted, 2,6- i Pr2-substituted phenyl (Dipp) system. In an attempt to prepare the extremely bulky amine [(ad)(2,6- i Pr2C6H3)NH] (ad=adamantyl) we found instead that the adamantyl group attacks the aromatic ring in the 4-position to form a new primary amine, (4-ad-2,6- i Pr2C6H2)NH2 (1) (ad-Dipp-NH2), characterized by normal techniques. Compound 1 could be converted into a Li salt by a 1:1 reaction with n BuLi, or converted into a more bulky silylamine, [(ad-Dipp)NH(SiMe3)] (3), by treatment with Me3SiCl. We have characterized the lithium salt by X-ray crystallography as the dimeric complex, [(ad-Dipp)NHLi(Et2O)]2 (2). The lithium amide can be used as a reagent towards metal halides, and we have discovered that its reaction with SnCl2 yields a compound with a tetrameric, [Sn–N]4 cubane-like cage structure. We have also demonstrated the ligand behavior of 3 by its reaction with Bu2Mg in THF to form a monomeric Mg-amide with two THF solvent molecules attached. These new ligands can provide advantages over conventional ligands in terms of improved solubility and ease of crystallization. [Copyright &y& Elsevier]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Inorganica Chimica Acta is the property of Elsevier B.V. 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=19468519
RecordInfo BibRecord:
  BibEntity:
    Identifiers:
      – Type: doi
        Value: 10.1016/j.ica.2005.04.032
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 7
        StartPage: 775
    Subjects:
      – SubjectFull: Ligands (Chemistry)
        Type: general
      – SubjectFull: Phenyl compounds
        Type: general
      – SubjectFull: Amines
        Type: general
      – SubjectFull: Crystallography
        Type: general
    Titles:
      – TitleFull: Two new bulky amido ligands useful for the preparation of metal complexes and examples of their reactivity
        Type: main
  BibRelationships:
    HasContributorRelationships:
      – PersonEntity:
          Name:
            NameFull: Tang, Yongjun
      – PersonEntity:
          Name:
            NameFull: Zakharov, Lev N.
      – PersonEntity:
          Name:
            NameFull: Rheingold, Arnold L.
      – PersonEntity:
          Name:
            NameFull: Kemp, Richard A.
    IsPartOfRelationships:
      – BibEntity:
          Dates:
            – D: 01
              M: 02
              Text: Feb2006
              Type: published
              Y: 2006
          Identifiers:
            – Type: issn-print
              Value: 00201693
          Numbering:
            – Type: volume
              Value: 359
            – Type: issue
              Value: 3
          Titles:
            – TitleFull: Inorganica Chimica Acta
              Type: main
ResultId 1