On the unprecedented level of dinitrogen activation in the calix[4]arene complex of Nb(iii)Electronic supplementary information (ESI) available. See DOI: 10.1039/c1dt11091h.
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| Title: | On the unprecedented level of dinitrogen activation in the calix[4]arene complex of Nb(iii)Electronic supplementary information (ESI) available. See DOI: 10.1039/c1dt11091h. |
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| Authors: | Terrett, R.1, Cavigliasso, G.1, Stranger, R.1, Yates, B. F.2 |
| Source: | Dalton Transactions: An International Journal of Inorganic Chemistry. Nov2011, Vol. 40 Issue 42, p11267-11275. 9p. |
| Subjects: | Niobium, Aromatic compounds, Hydroxides, Chemical bonds, Crystallography, Metal complexes |
| Abstract: | The calix[4]arene niobium(iii) complex ([L]Nb–NN–Nb[L] where [L] = p-tert-butylcalix[4]arene), reported to bind N2in a μ2-linear dimeric capacity and to activate the N2triple bond to 1.39 Å, corresponding to the longest N2bond known in the end-on coordination mode, was subjected to a computational investigation involving both density functional and wavefunction based methods to establish the basis for the unprecedented level of activation. Replacement of the calix[4]arene ligand with hydroxide or methoxide ligands reveals that the organic backbone structure of the calix[4]arene ligand exerts negligible electronic influence over the metal centre, serving only to geometrically constrain the coordinating phenoxide groups. A fragment bonding analysis shows that metal-to-dinitrogen π*backbonding is the principal Nb–N interaction, providing a strong electronic basis for analogy with other well-characterised three- and four-coordinate complexes which bind N2end-on. While the calculated structure of the metallacalix[4]arene unit is reproduced with high accuracy, as is also the Nb–Nb separation, the calculated equilibrium geometry of the complex under a variety of conditions consistently indicates against a 1.39 Å activation of the N2bond. Instead, the calculated N–N distances fall within the range 1.26–1.30 Å, a result concordant with closely related three- and four-coordinate μ2–N2complexes as well as predictions derived from trends in N–N stretching frequency for a number of crystallographically characterized linear N2activators. A number of potential causes for this bond length discrepancy are explored. [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 |
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| Header | DbId: egs DbLabel: Engineering Source An: 66716848 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: On the unprecedented level of dinitrogen activation in the calix[4]arene complex of Nb(iii)Electronic supplementary information (ESI) available. See DOI: 10.1039/c1dt11091h. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Terrett%2C+R%2E%22">Terrett, R.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Cavigliasso%2C+G%2E%22">Cavigliasso, G.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Stranger%2C+R%2E%22">Stranger, R.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Yates%2C+B%2E+F%2E%22">Yates, B. F.</searchLink><relatesTo>2</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>. Nov2011, Vol. 40 Issue 42, p11267-11275. 9p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Niobium%22">Niobium</searchLink><br /><searchLink fieldCode="DE" term="%22Aromatic+compounds%22">Aromatic compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Hydroxides%22">Hydroxides</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+bonds%22">Chemical bonds</searchLink><br /><searchLink fieldCode="DE" term="%22Crystallography%22">Crystallography</searchLink><br /><searchLink fieldCode="DE" term="%22Metal+complexes%22">Metal complexes</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: The calix[4]arene niobium(iii) complex ([L]Nb–NN–Nb[L] where [L] = p-tert-butylcalix[4]arene), reported to bind N2in a μ2-linear dimeric capacity and to activate the N2triple bond to 1.39 Å, corresponding to the longest N2bond known in the end-on coordination mode, was subjected to a computational investigation involving both density functional and wavefunction based methods to establish the basis for the unprecedented level of activation. Replacement of the calix[4]arene ligand with hydroxide or methoxide ligands reveals that the organic backbone structure of the calix[4]arene ligand exerts negligible electronic influence over the metal centre, serving only to geometrically constrain the coordinating phenoxide groups. A fragment bonding analysis shows that metal-to-dinitrogen π*backbonding is the principal Nb–N interaction, providing a strong electronic basis for analogy with other well-characterised three- and four-coordinate complexes which bind N2end-on. While the calculated structure of the metallacalix[4]arene unit is reproduced with high accuracy, as is also the Nb–Nb separation, the calculated equilibrium geometry of the complex under a variety of conditions consistently indicates against a 1.39 Å activation of the N2bond. Instead, the calculated N–N distances fall within the range 1.26–1.30 Å, a result concordant with closely related three- and four-coordinate μ2–N2complexes as well as predictions derived from trends in N–N stretching frequency for a number of crystallographically characterized linear N2activators. A number of potential causes for this bond length discrepancy are explored. [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/c1dt11091h Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 9 StartPage: 11267 Subjects: – SubjectFull: Niobium Type: general – SubjectFull: Aromatic compounds Type: general – SubjectFull: Hydroxides Type: general – SubjectFull: Chemical bonds Type: general – SubjectFull: Crystallography Type: general – SubjectFull: Metal complexes Type: general Titles: – TitleFull: On the unprecedented level of dinitrogen activation in the calix[4]arene complex of Nb(iii)Electronic supplementary information (ESI) available. See DOI: 10.1039/c1dt11091h. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Terrett, R. – PersonEntity: Name: NameFull: Cavigliasso, G. – PersonEntity: Name: NameFull: Stranger, R. – PersonEntity: Name: NameFull: Yates, B. F. IsPartOfRelationships: – BibEntity: Dates: – D: 14 M: 11 Text: Nov2011 Type: published Y: 2011 Identifiers: – Type: issn-print Value: 14779226 Numbering: – Type: volume Value: 40 – Type: issue Value: 42 Titles: – TitleFull: Dalton Transactions: An International Journal of Inorganic Chemistry Type: main |
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