Structures, Metallophilic Interactions and Electronic Excitation Energy of Linear Metal Chain Complexes PdmPtn[PH2(CH2PH)m+n-2CH2PH2]3, A Theoretical Investigation

Publication date: Available online 21 January 2019Source: Computational and Theoretical ChemistryAuthor(s): Mingrui Shen, Congjie ZhangAbstractThe structures, metallophilic interactions and electronic excitation energy of linear metal chain complexes PdmPtn[PH2(CH2PH)m+n-2CH2PH2]3 (m+n=2-5) (1-18) have been investigated by using MP2 and density functional theory (DFT) methods. Calculated results indicated that geometries of PdmPtn(PH2CH2PH2)3 (m+n=2) (1-3) optimized by SVWN5 method are well consistent with those by MP2 method and experiment. Then, SVWN5 functional was used to the investigation of the large system of PdmPtn[PH2(CH2PH)m+n-2CH2PH2]3 complexes. The lowest energy structures of complexes 1-18 optimized by SVWN5 method are singlet. The lengths of Pd∙∙∙Pd and Pt∙∙∙Pt of Pdm[PH2(CH2PH)m-2CH2PH2]3 (m>2) and Ptn[PH2(CH2PH)n-2CH2PH2]3 (n>2) complexes at SVWN5 level are shorter than those of Pd2(PH2CH2PH2)3 and Pt2(PH2CH2PH2)3, indicating the interactions of Pd∙∙∙Pd and Pt∙∙∙Pt increase with the increase of the size of Pdm[PH2(CH2PH)m-2CH2PH2]3 and Ptn[PH2(CH2PH)n-2CH2PH2]3 complexes. Pd atoms in the mixed PdmPtn[PH2(CH2PH)m+n-2CH2PH2]3 complexes are favorable to locate at the ends of the metal chain. The lengths of Pd∙∙∙Pd and Pt∙∙∙Pt bonds in the mixed metal chain of PdmPtn[PH2(CH2PH)m+n-2CH2PH2]3 complexes have no significantly variation compared with those of the Pdm+n[PH2(CH2PH)m+n-2CH2PH2]3 and Ptm+n[PH2(CH2PH)m+n-2CH2PH2]3. But, ...

Source: Computational and Theoretical Chemistry - January 21, 2019 Category: Chemistry Source Type: research