Molecules 2013, 18(10), 12687-12706; doi:10.3390/molecules181012687
Article

Orbital Interaction and Electron Density Transfer in PdII([9]aneB2A)L2 Complexes: Theoretical Approaches

1 Department of Chemistry Education and Research Institute of Natural Science, Educational Research Institute Teachers College, Gyeongsang National University, Jinju 660-701, Korea 2 Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 660-701, Korea 3 Division of High-Technology Materials Research, Korea Basic Science Institute, Busan 618-230, Korea
* Author to whom correspondence should be addressed.
Received: 29 July 2013; in revised form: 13 September 2013 / Accepted: 29 September 2013 / Published: 14 October 2013
(This article belongs to the Special Issue Macrocyclic Chemistry)
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Abstract: 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.
Keywords: macrocyclic tridentate; position selectivity; steric and electronic effects; orbital interaction; geometric configuration

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MDPI and ACS Style

Kwak, O.K.; Arooj, M.; Yoon, Y.-J.; Jeong, E.D.; Park, J.K. Orbital Interaction and Electron Density Transfer in PdII([9]aneB2A)L2 Complexes: Theoretical Approaches. Molecules 2013, 18, 12687-12706.

AMA Style

Kwak OK, Arooj M, Yoon Y-J, Jeong ED, Park JK. Orbital Interaction and Electron Density Transfer in PdII([9]aneB2A)L2 Complexes: Theoretical Approaches. Molecules. 2013; 18(10):12687-12706.

Chicago/Turabian Style

Kwak, Ock K.; Arooj, Mahreen; Yoon, Yong-Jin; Jeong, Euh D.; Park, Jong K. 2013. "Orbital Interaction and Electron Density Transfer in PdII([9]aneB2A)L2 Complexes: Theoretical Approaches." Molecules 18, no. 10: 12687-12706.

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