The Conjugation Stress of Ligand via Metal Core as the Cause of Changes in the Reactivity of Coordinated 1-Hetero-1,3-Dienes
Using quantum-chemical calculations carried out for interpretation of the experimentally discovered reactivity of 1-hetero-1,3-dienes that are mono- and bidentally coordinated with the transition metal core, we have revealed that the difference in hydrophosphorylation directions of the free organic...
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Kazan Federal University
2016-06-01
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| Series: | Учёные записки Казанского университета: Серия Естественные науки |
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| Online Access: | http://kpfu.ru/portal/docs/F1175176632/158_2_est_1.pdf |
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| author | A.I. Kuramshin E.V. Kolpakova R.A. Cherkasov V.I. Galkin |
| author_facet | A.I. Kuramshin E.V. Kolpakova R.A. Cherkasov V.I. Galkin |
| author_sort | A.I. Kuramshin |
| collection | DOAJ |
| description | Using quantum-chemical calculations carried out for interpretation of the experimentally discovered reactivity of 1-hetero-1,3-dienes that are mono- and bidentally coordinated with the transition metal core, we have revealed that the difference in hydrophosphorylation directions of the free organic molecule and the same molecule involved in the coordination sphere of the transition metal can be explained by either weakening or complete loss of conjugation between the C=C and C=X fragments as a result of coordination.
In the case of monodentate coordination of heterodiene with the transition metal according to the eta(2)(C,C)-type, the conjugation weakening is suggested to be maximum for the transition metal characterized by the minimum electronegativity, which predetermines the increased contribution of the metalcyclopropane resonance structure into the general bonding mode. Organometallic compounds having the heterodiene ligand bidentally coordinated demonstrate the conjugation weakening parallel to the metal radius. |
| format | Article |
| id | doaj-art-f04894a4749c4d36bc09eb0e9220346f |
| institution | Kabale University |
| issn | 1815-6169 2500-218X |
| language | English |
| publishDate | 2016-06-01 |
| publisher | Kazan Federal University |
| record_format | Article |
| series | Учёные записки Казанского университета: Серия Естественные науки |
| spelling | doaj-art-f04894a4749c4d36bc09eb0e9220346f2025-01-02T15:06:44ZengKazan Federal UniversityУчёные записки Казанского университета: Серия Естественные науки1815-61692500-218X2016-06-011582176186The Conjugation Stress of Ligand via Metal Core as the Cause of Changes in the Reactivity of Coordinated 1-Hetero-1,3-DienesA.I. Kuramshin0E.V. Kolpakova1R.A. Cherkasov2V.I. Galkin3Kazan Federal University, Kazan, 420008 RussiaKazan Federal University, Kazan, 420008 RussiaKazan Federal University, Kazan, 420008 RussiaKazan Federal University, Kazan, 420008 RussiaUsing quantum-chemical calculations carried out for interpretation of the experimentally discovered reactivity of 1-hetero-1,3-dienes that are mono- and bidentally coordinated with the transition metal core, we have revealed that the difference in hydrophosphorylation directions of the free organic molecule and the same molecule involved in the coordination sphere of the transition metal can be explained by either weakening or complete loss of conjugation between the C=C and C=X fragments as a result of coordination. In the case of monodentate coordination of heterodiene with the transition metal according to the eta(2)(C,C)-type, the conjugation weakening is suggested to be maximum for the transition metal characterized by the minimum electronegativity, which predetermines the increased contribution of the metalcyclopropane resonance structure into the general bonding mode. Organometallic compounds having the heterodiene ligand bidentally coordinated demonstrate the conjugation weakening parallel to the metal radius.http://kpfu.ru/portal/docs/F1175176632/158_2_est_1.pdfquantum-chemical calculationsmetal-organic derivatives of chromium group metalsdensity functional (DFT)conjugationstress energy |
| spellingShingle | A.I. Kuramshin E.V. Kolpakova R.A. Cherkasov V.I. Galkin The Conjugation Stress of Ligand via Metal Core as the Cause of Changes in the Reactivity of Coordinated 1-Hetero-1,3-Dienes Учёные записки Казанского университета: Серия Естественные науки quantum-chemical calculations metal-organic derivatives of chromium group metals density functional (DFT) conjugation stress energy |
| title | The Conjugation Stress of Ligand via Metal Core as the Cause of Changes in the Reactivity of Coordinated 1-Hetero-1,3-Dienes |
| title_full | The Conjugation Stress of Ligand via Metal Core as the Cause of Changes in the Reactivity of Coordinated 1-Hetero-1,3-Dienes |
| title_fullStr | The Conjugation Stress of Ligand via Metal Core as the Cause of Changes in the Reactivity of Coordinated 1-Hetero-1,3-Dienes |
| title_full_unstemmed | The Conjugation Stress of Ligand via Metal Core as the Cause of Changes in the Reactivity of Coordinated 1-Hetero-1,3-Dienes |
| title_short | The Conjugation Stress of Ligand via Metal Core as the Cause of Changes in the Reactivity of Coordinated 1-Hetero-1,3-Dienes |
| title_sort | conjugation stress of ligand via metal core as the cause of changes in the reactivity of coordinated 1 hetero 1 3 dienes |
| topic | quantum-chemical calculations metal-organic derivatives of chromium group metals density functional (DFT) conjugation stress energy |
| url | http://kpfu.ru/portal/docs/F1175176632/158_2_est_1.pdf |
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