CAS OpenIR  > 中科院上海应用物理研究所2011-2020年
End-On Cyanogen Complexes of Iridium, Palladium, and Platinum
Chen, XT; Xiong, ZX; Andrews, L; Gong, Y
2020
Source PublicationINORGANIC CHEMISTRY
ISSN0020-1669
Volume59Issue:9Pages:6489-6495
Subtype期刊论文
AbstractThe cyanogen complexes of iridium, palladium, and platinum were prepared via the reactions of noble metal atoms with cyanogen in argon matrixes, and the product structures were determined by infrared spectroscopy and density functional theory calculations. These complexes were predicted to possess linear geometries with the metal center coordinated by the nitrogen atom of cyanogen in end-on fashions. On the basis of the B3LYP calculations, doublet, singlet, and singlet spin states are most stable for [Ir(NCCN)], [Pd(NCCN)], and [Pt(NCCN)]. Bonding analysis revealed the presence of electron donation from the polarized sigma - orbital of cyanogen into the empty metal d(z)(2) orbital and back-donation from the metal d(xz/yz) orbitals to the 2 pi(u) orbitals of cyanogen, the latter of which destabilizes the C-N bond and stabilizes the C-C bond. Such an effect causes an increase in C-N bond length by 0.01-0.015 angstrom and a decrease in C-C bond length by 0.013-0.02 angstrom for noble-metal-cyanogen complexes in comparison to the same bond in neutral cyanogen, and this is also consistent with the changes in vibrational frequencies. Although [Ir(NCCN)], [Pd(NCCN)], and [Pt(NCCN)] were formed spontaneously during sample annealing, neither cyanide nor isocyanide product was observed in the experiments, which is different from the cases of early transition, lanthanide, and actinide metals.
KeywordMATRIX INFRARED-SPECTRA ANION PHOTOELECTRON-SPECTROSCOPY DENSITY-FUNCTIONAL CALCULATIONS LASER-ABLATED PLATINUM THEORETICAL INVESTIGATIONS COORDINATION CHEMISTRY HYDROGEN-CYANIDE BASIS-SETS ATOMS NICKEL
DOI10.1021/acs.inorgchem.0c00582
Indexed BySCI
Language英语
Citation statistics
Document Type期刊论文
Identifierhttp://ir.sinap.ac.cn/handle/331007/32850
Collection中科院上海应用物理研究所2011-2020年
Affiliation1.Chinese Acad Sci, Shanghai Inst Appl Phys, Dept Radiochem, Shanghai 201800, Peoples R China
2.Univ Virginia, Dept Chem, Charlottesville, VA 22904 USA
3.Univ Chinese Acad Sci, Sch Nucl Sci & Technol, Beijing 100049, Peoples R China
Recommended Citation
GB/T 7714
Chen, XT,Xiong, ZX,Andrews, L,et al. End-On Cyanogen Complexes of Iridium, Palladium, and Platinum[J]. INORGANIC CHEMISTRY,2020,59(9):6489-6495.
APA Chen, XT,Xiong, ZX,Andrews, L,&Gong, Y.(2020).End-On Cyanogen Complexes of Iridium, Palladium, and Platinum.INORGANIC CHEMISTRY,59(9),6489-6495.
MLA Chen, XT,et al."End-On Cyanogen Complexes of Iridium, Palladium, and Platinum".INORGANIC CHEMISTRY 59.9(2020):6489-6495.
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