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The Vibrational Spectra of the Cyanide Ligand Revisited: Double Bridging Cyanides
Author(s) -
Kettle Sidney F. A.,
Diana Eliano,
Marchese Edoardo M. C.,
Boccaleri Enrico,
Croce Gianluca,
Sheng Tianlu,
Stanghellini Pier Luigi
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201000265
Subject(s) - chemistry , prussian blue , crystallography , cyanide , antibonding molecular orbital , raman spectroscopy , infrared spectroscopy , metal , crystal structure , spectral line , infrared , ligand (biochemistry) , molecular vibration , computational chemistry , molecule , inorganic chemistry , electrochemistry , organic chemistry , physics , electrode , quantum mechanics , astronomy , atomic orbital , optics , electron , biochemistry , receptor
The vibrational behaviour of complexes of general formula [(ML 5 CN) 2 M′L′ 4 ] with either a cis or trans geometry has been studied. The ν(CN) modes have been assigned on the basis of both infrared and Raman intensities. The CN vibrators are but weakly coupled, particularly so in the cis arrangement. The spectroscopic analysis offers insights into the interpretation of the spectra of Prussian Blue species as cis and trans M–CN–M′–NC–M complexes may be regarded as building blocks of Prussian Blue. The structure of the complex [(CO) 5 MoCNNi(Bipy) 2 NCMo(CO) 5 ] confirms the expected cis geometry of the metal core. The complex [Cp(dppe)FeNCRu(4‐EtPy) 4 CNFeCp(dppe)] 3+ [PF 6 – ] 3 was prepared by oxidising the reduced form (2+ cation) and its crystal structure was determined and compared with that of the starting complex. Analysis of the structural and spectroscopic data led to the conclusion that the two iron atoms in the oxidised form have different charges and that the vibrations of the two CN groups are essentially independent. DFT calculations indicate that although π‐bonding and antibonding occur, electrostatic effects (as described by the IVSE model) are probably more important.