Orbital Interaction and Electron Density Transfer in PdII([9]aneB2A)L2 Complexes: Theoretical Approaches
The geometric structures of Pd-complexes {Pd([9]aneB2A)L2 and Pd([9]aneBAB)L2 where A = P, S; B = N; L = PH3, P(CH3)3, Cl−}, their selective orbital interaction towards equatorial or axial (soft A…Pd) coordination of macrocyclic [9]aneB2A tridentate to PdL2, and electron density transfer from the el...
| Main Authors: | , , , , |
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| Format: | Journal Article |
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M D P I AG
2013
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| Online Access: | http://hdl.handle.net/20.500.11937/16654 |
| _version_ | 1848749237954674688 |
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| author | Keum Kwak, Ock Arooj, Mahreen Yoon, Yong-Jin Duck Jeong, Euh Keun Park, Jong |
| author_facet | Keum Kwak, Ock Arooj, Mahreen Yoon, Yong-Jin Duck Jeong, Euh Keun Park, Jong |
| author_sort | Keum Kwak, Ock |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | The geometric structures of Pd-complexes {Pd([9]aneB2A)L2 and Pd([9]aneBAB)L2 where A = P, S; B = N; L = PH3, P(CH3)3, Cl−}, their selective orbital interaction towards equatorial or axial (soft A…Pd) coordination of macrocyclic [9]aneB2A tridentate to PdL2, and electron density transfer from the electron-rich trans L-ligand to the low-lying unfilled a1g(5s)-orbital of PdL2 were investigated using B3P86/lanl2DZ for Pd and 6-311+G** for other atoms. The pentacoordinate endo-[Pd([9]aneB2A)(L-donor)2]2+ complex with an axial (soft A--Pd) quasi-bond was optimized for stability. The fifth (soft A--Pd) quasi-bond between the σ-donor of soft A and the partially unfilled a1g(5s)-orbital of PdL2 was formed. The pentacoordinate endo-Pd([9]aneB2A)(L-donor)2]2+ complex has been found to be more stable than the corresponding tetracoordinate endo-Pd complexes. Except for the endo-Pd pentacoordinates, the tetracoordinate Pd([9]aneBAB)L2 complex with one equatorial (soft A-Pd) bond is found to be more stable than the Pd([9]aneB2A)L2 isomer without the equatorial (A-Pd) bond. In particular, the geometric configuration of endo-[Pd([9]anePNP)(L-donor)2]2+ could not be optimized. |
| first_indexed | 2025-11-14T07:17:45Z |
| format | Journal Article |
| id | curtin-20.500.11937-16654 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T07:17:45Z |
| publishDate | 2013 |
| publisher | M D P I AG |
| recordtype | eprints |
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| spelling | curtin-20.500.11937-166542017-09-13T15:43:30Z Orbital Interaction and Electron Density Transfer in PdII([9]aneB2A)L2 Complexes: Theoretical Approaches Keum Kwak, Ock Arooj, Mahreen Yoon, Yong-Jin Duck Jeong, Euh Keun Park, Jong geometric configuration orbital interaction steric and electronic effects position selectivity macrocyclic tridentate The geometric structures of Pd-complexes {Pd([9]aneB2A)L2 and Pd([9]aneBAB)L2 where A = P, S; B = N; L = PH3, P(CH3)3, Cl−}, their selective orbital interaction towards equatorial or axial (soft A…Pd) coordination of macrocyclic [9]aneB2A tridentate to PdL2, and electron density transfer from the electron-rich trans L-ligand to the low-lying unfilled a1g(5s)-orbital of PdL2 were investigated using B3P86/lanl2DZ for Pd and 6-311+G** for other atoms. The pentacoordinate endo-[Pd([9]aneB2A)(L-donor)2]2+ complex with an axial (soft A--Pd) quasi-bond was optimized for stability. The fifth (soft A--Pd) quasi-bond between the σ-donor of soft A and the partially unfilled a1g(5s)-orbital of PdL2 was formed. The pentacoordinate endo-Pd([9]aneB2A)(L-donor)2]2+ complex has been found to be more stable than the corresponding tetracoordinate endo-Pd complexes. Except for the endo-Pd pentacoordinates, the tetracoordinate Pd([9]aneBAB)L2 complex with one equatorial (soft A-Pd) bond is found to be more stable than the Pd([9]aneB2A)L2 isomer without the equatorial (A-Pd) bond. In particular, the geometric configuration of endo-[Pd([9]anePNP)(L-donor)2]2+ could not be optimized. 2013 Journal Article http://hdl.handle.net/20.500.11937/16654 10.3390/molecules181012687 M D P I AG fulltext |
| spellingShingle | geometric configuration orbital interaction steric and electronic effects position selectivity macrocyclic tridentate Keum Kwak, Ock Arooj, Mahreen Yoon, Yong-Jin Duck Jeong, Euh Keun Park, Jong Orbital Interaction and Electron Density Transfer in PdII([9]aneB2A)L2 Complexes: Theoretical Approaches |
| title | Orbital Interaction and Electron Density Transfer in PdII([9]aneB2A)L2 Complexes: Theoretical Approaches |
| title_full | Orbital Interaction and Electron Density Transfer in PdII([9]aneB2A)L2 Complexes: Theoretical Approaches |
| title_fullStr | Orbital Interaction and Electron Density Transfer in PdII([9]aneB2A)L2 Complexes: Theoretical Approaches |
| title_full_unstemmed | Orbital Interaction and Electron Density Transfer in PdII([9]aneB2A)L2 Complexes: Theoretical Approaches |
| title_short | Orbital Interaction and Electron Density Transfer in PdII([9]aneB2A)L2 Complexes: Theoretical Approaches |
| title_sort | orbital interaction and electron density transfer in pdii([9]aneb2a)l2 complexes: theoretical approaches |
| topic | geometric configuration orbital interaction steric and electronic effects position selectivity macrocyclic tridentate |
| url | http://hdl.handle.net/20.500.11937/16654 |