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

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)
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
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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