Microwave spectra, ab initio and DFT calculations and molecular structure for (η7-cycloheptatriene)Ti(η5-cyclopentadienyl) and (η7-cycloheptatriene)Cr(η5-cyclopentadienyl)
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| Title: | Microwave spectra, ab initio and DFT calculations and molecular structure for (η7-cycloheptatriene)Ti(η5-cyclopentadienyl) and (η7-cycloheptatriene)Cr(η5-cyclopentadienyl) |
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| Authors: | Daly, Adam M.1, Lavin, Catherine M.1, Weidenschilling, Erika S., Holden, Alison M., Kukolich, Stephen G. kukolich@u.arizona.edu |
| Source: | Journal of Molecular Spectroscopy. May2011, Vol. 267 Issue 1/2, p172-177. 6p. |
| Subjects: | Microwave spectroscopy, Molecular structure, Cyclic compounds, Organometallic compounds, Titanium compounds, Molecular rotation, Density functionals |
| Abstract: | Abstract: Microwave spectra of 1-d-(η7-cycloheptatriene)48Ti(η5-cyclopentadienyl) (CHT–Ti–Cp) and two singly substituted 13C isotopomers were measured and gas phase structural parameters were determined. Rotational transitions were also measured for (η7-cycloheptatriene)52Cr(η5-cyclopentadienyl). Rotational constants for the Ti complex were found to be A =1720(4)MHz, B =769.269(1)MHz and C =766.131(1)MHz and for [13CC6H7–48Ti–C5H5], A =1773(2)MHz, B =769.6931(4)MHz and C =761.1789(5)MHz and for [1-d-C7H6 48TiC5H5] and A =1270(5)MHz, B =767.0142(9)MHz and C =765.323(1)MHz for [C7H7 48Ti13CC4H5]. A structural analysis for the (CHT–Ti–Cp) data showed that the cycloheptatriene ring protons droop towards titanium as predicted by DFT and MP2 calculations. The droop of the protons toward the metal was experimentally determined to be 8.0(2)° out of the plane of the cycloheptatriene ring. The ring center distance to titanium was found to be 2.01(3)Å for Ti–Cp and 1.48(3)Å for Ti–CHT using a least squares fit to the measured rotational constants and fixing many of the structural parameters to the calculated values. The spectrum of the normal isotopomer (η7-cycloheptatriene)Ti(η5-cyclopentadienyl) was re-measured and a discussion of the possible 47Ti quadrupole coupling constants is presented. The chromium analog K =0 spectrum was analyzed to obtain B =851.229MHz, and D J =0.028(6)kHz. Results from structure calculations are reported and discussed for (CHT–M–Cp) complexes with M=Ti, Cr, Zr, Hf, Mo, W using MP2, B3PW91 and B3LYP methods. [Copyright &y& Elsevier] |
| Copyright of Journal of Molecular Spectroscopy is the property of Academic Press Inc. 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: 61243927 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Microwave spectra, ab initio and DFT calculations and molecular structure for (η<superscript>7</superscript>-cycloheptatriene)Ti(η<superscript>5</superscript>-cyclopentadienyl) and (η<superscript>7</superscript>-cycloheptatriene)Cr(η<superscript>5</superscript>-cyclopentadienyl) – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Daly%2C+Adam+M%2E%22">Daly, Adam M.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Lavin%2C+Catherine+M%2E%22">Lavin, Catherine M.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Weidenschilling%2C+Erika+S%2E%22">Weidenschilling, Erika S.</searchLink><br /><searchLink fieldCode="AR" term="%22Holden%2C+Alison+M%2E%22">Holden, Alison M.</searchLink><br /><searchLink fieldCode="AR" term="%22Kukolich%2C+Stephen+G%2E%22">Kukolich, Stephen G.</searchLink><i> kukolich@u.arizona.edu</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+Molecular+Spectroscopy%22">Journal of Molecular Spectroscopy</searchLink>. May2011, Vol. 267 Issue 1/2, p172-177. 6p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Microwave+spectroscopy%22">Microwave spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+structure%22">Molecular structure</searchLink><br /><searchLink fieldCode="DE" term="%22Cyclic+compounds%22">Cyclic compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Organometallic+compounds%22">Organometallic compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Titanium+compounds%22">Titanium compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+rotation%22">Molecular rotation</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functionals%22">Density functionals</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Abstract: Microwave spectra of 1-d-(η7-cycloheptatriene)48Ti(η5-cyclopentadienyl) (CHT–Ti–Cp) and two singly substituted 13C isotopomers were measured and gas phase structural parameters were determined. Rotational transitions were also measured for (η7-cycloheptatriene)52Cr(η5-cyclopentadienyl). Rotational constants for the Ti complex were found to be A =1720(4)MHz, B =769.269(1)MHz and C =766.131(1)MHz and for [13CC6H7–48Ti–C5H5], A =1773(2)MHz, B =769.6931(4)MHz and C =761.1789(5)MHz and for [1-d-C7H6 48TiC5H5] and A =1270(5)MHz, B =767.0142(9)MHz and C =765.323(1)MHz for [C7H7 48Ti13CC4H5]. A structural analysis for the (CHT–Ti–Cp) data showed that the cycloheptatriene ring protons droop towards titanium as predicted by DFT and MP2 calculations. The droop of the protons toward the metal was experimentally determined to be 8.0(2)° out of the plane of the cycloheptatriene ring. The ring center distance to titanium was found to be 2.01(3)Å for Ti–Cp and 1.48(3)Å for Ti–CHT using a least squares fit to the measured rotational constants and fixing many of the structural parameters to the calculated values. The spectrum of the normal isotopomer (η7-cycloheptatriene)Ti(η5-cyclopentadienyl) was re-measured and a discussion of the possible 47Ti quadrupole coupling constants is presented. The chromium analog K =0 spectrum was analyzed to obtain B =851.229MHz, and D J =0.028(6)kHz. Results from structure calculations are reported and discussed for (CHT–M–Cp) complexes with M=Ti, Cr, Zr, Hf, Mo, W using MP2, B3PW91 and B3LYP methods. [Copyright &y& Elsevier] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of Molecular Spectroscopy is the property of Academic Press Inc. 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: 10.1016/j.jms.2011.03.013 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 6 StartPage: 172 Subjects: – SubjectFull: Microwave spectroscopy Type: general – SubjectFull: Molecular structure Type: general – SubjectFull: Cyclic compounds Type: general – SubjectFull: Organometallic compounds Type: general – SubjectFull: Titanium compounds Type: general – SubjectFull: Molecular rotation Type: general – SubjectFull: Density functionals Type: general Titles: – TitleFull: Microwave spectra, ab initio and DFT calculations and molecular structure for (η7-cycloheptatriene)Ti(η5-cyclopentadienyl) and (η7-cycloheptatriene)Cr(η5-cyclopentadienyl) Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Daly, Adam M. – PersonEntity: Name: NameFull: Lavin, Catherine M. – PersonEntity: Name: NameFull: Weidenschilling, Erika S. – PersonEntity: Name: NameFull: Holden, Alison M. – PersonEntity: Name: NameFull: Kukolich, Stephen G. IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 05 Text: May2011 Type: published Y: 2011 Identifiers: – Type: issn-print Value: 00222852 Numbering: – Type: volume Value: 267 – Type: issue Value: 1/2 Titles: – TitleFull: Journal of Molecular Spectroscopy Type: main |
| ResultId | 1 |
