Sm(ii) reduction chemistry of heteroalkynes: stable adducts, reductive coupling, reductive C–C/C–N bond cleavage and trapping of the tert-butyl fragment with bulky nitriles, phosphaalkynes and isonitrilesCCDC reference numbers 765856–765859for 2–5, respectively. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c002778b
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| Title: | Sm(ii) reduction chemistry of heteroalkynes: stable adducts, reductive coupling, reductive C–C/C–N bond cleavage and trapping of the tert-butyl fragment with bulky nitriles, phosphaalkynes and isonitrilesCCDC reference numbers 765856–765859for 2–5, respectively. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c002778b |
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| Authors: | Gardiner, Michael G.1, James, Adam N.1, Jones, Cameron1, Schulten, Christian1 |
| Source: | Dalton Transactions: An International Journal of Inorganic Chemistry. Jul2010, Vol. 39 Issue 29, p6864-6870. 7p. |
| Subjects: | Chemical reduction, Alkynes, Scission (Chemistry), Nitriles, Isocyanides, Reactivity (Chemistry), Stereoisomers, Metal complexes |
| Abstract: | Reactions of a dimetallated N,N′-dimethyl substituted porphyrinogen Sm(ii) complex with a series of t-butyl substituted heteroalkynes affords a diverse range of reactivity. The phosphaalkyne t-BuCP gives a dinuclear Sm(iii) P–P reductively coupled complex of (t-BuCPPC-t-Bu)2−featuring a new μ-η2(1,2-C,P) binding mode. In contrast, the nitrile aza analogue t-BuCN forms Sm(ii) adducts that undergo reductive C–C bond cleavage at elevated temperatures to afford a trimeric Sm(iii) cyanide (μ-CN−) complex. The isomeric isonitrile t-BuNC undergoes the related reductive C–N bond cleavage reactivity at milder temperatures, allowing the trapping of the tert-butyl fragment as a Sm(iii) η2-iminoacyl (t-BuCN-t-Bu)−complex. [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 |
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| Header | DbId: egs DbLabel: Engineering Source An: 52347696 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Sm(ii) reduction chemistry of heteroalkynes: stable adducts, reductive coupling, reductive C–C/C–N bond cleavage and trapping of the tert-butyl fragment with bulky nitriles, phosphaalkynes and isonitrilesCCDC reference numbers 765856–765859for 2–5, respectively. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c002778b – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Gardiner%2C+Michael+G%2E%22">Gardiner, Michael G.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22James%2C+Adam+N%2E%22">James, Adam N.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Jones%2C+Cameron%22">Jones, Cameron</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Schulten%2C+Christian%22">Schulten, Christian</searchLink><relatesTo>1</relatesTo> – 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>. Jul2010, Vol. 39 Issue 29, p6864-6870. 7p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Chemical+reduction%22">Chemical reduction</searchLink><br /><searchLink fieldCode="DE" term="%22Alkynes%22">Alkynes</searchLink><br /><searchLink fieldCode="DE" term="%22Scission+%28Chemistry%29%22">Scission (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Nitriles%22">Nitriles</searchLink><br /><searchLink fieldCode="DE" term="%22Isocyanides%22">Isocyanides</searchLink><br /><searchLink fieldCode="DE" term="%22Reactivity+%28Chemistry%29%22">Reactivity (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Stereoisomers%22">Stereoisomers</searchLink><br /><searchLink fieldCode="DE" term="%22Metal+complexes%22">Metal complexes</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Reactions of a dimetallated N,N′-dimethyl substituted porphyrinogen Sm(ii) complex with a series of t-butyl substituted heteroalkynes affords a diverse range of reactivity. The phosphaalkyne t-BuCP gives a dinuclear Sm(iii) P–P reductively coupled complex of (t-BuCPPC-t-Bu)2−featuring a new μ-η2(1,2-C,P) binding mode. In contrast, the nitrile aza analogue t-BuCN forms Sm(ii) adducts that undergo reductive C–C bond cleavage at elevated temperatures to afford a trimeric Sm(iii) cyanide (μ-CN−) complex. The isomeric isonitrile t-BuNC undergoes the related reductive C–N bond cleavage reactivity at milder temperatures, allowing the trapping of the tert-butyl fragment as a Sm(iii) η2-iminoacyl (t-BuCN-t-Bu)−complex. [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.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1039/c002778b Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 7 StartPage: 6864 Subjects: – SubjectFull: Chemical reduction Type: general – SubjectFull: Alkynes Type: general – SubjectFull: Scission (Chemistry) Type: general – SubjectFull: Nitriles Type: general – SubjectFull: Isocyanides Type: general – SubjectFull: Reactivity (Chemistry) Type: general – SubjectFull: Stereoisomers Type: general – SubjectFull: Metal complexes Type: general Titles: – TitleFull: Sm(ii) reduction chemistry of heteroalkynes: stable adducts, reductive coupling, reductive C–C/C–N bond cleavage and trapping of the tert-butyl fragment with bulky nitriles, phosphaalkynes and isonitrilesCCDC reference numbers 765856–765859for 2–5, respectively. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c002778b Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Gardiner, Michael G. – PersonEntity: Name: NameFull: James, Adam N. – PersonEntity: Name: NameFull: Jones, Cameron – PersonEntity: Name: NameFull: Schulten, Christian IsPartOfRelationships: – BibEntity: Dates: – D: 13 M: 07 Text: Jul2010 Type: published Y: 2010 Identifiers: – Type: issn-print Value: 14779226 Numbering: – Type: volume Value: 39 – Type: issue Value: 29 Titles: – TitleFull: Dalton Transactions: An International Journal of Inorganic Chemistry Type: main |
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