Metal isotope effect on metal-ligand vibrations. II. Tris complexes of 2,2'-bipyridine and 1,10-phenanthroline

Raman spectra of two spin-transition polymers, [Fe(NH 2 trz) 3 ](ClO 4 ) 2 and [Fe(Htrz) 3 ](ClO 4 ) 2 , where NH 2 trz = 4-NH 2 -1,2,4-triazole and Htrz = 1-H-1,2,4-triazole, were investigated. The low-temperature high-spin to low-spin phase transition of [Fe(NH 2 trz) 3 ](ClO 4 / 2 is reported. The increasing intensity of the Fe-N stretching band, which appears in the spectrum of the low-spin state, is plotted against temperature to obtain a representative transition curve.

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“…Similar assignments were made by Hutchinson et al 19 and similar values were also observed in the infrared study of [Fe(Htrz) 3 ](ClO 4 2 . 12…”

Section: Metal-ligand Vibrationssupporting

confidence: 87%

Low‐wavenumber Raman spectra of the spin‐transition complexes [Fe(NH₂ trz)₃](ClO₄)₂ and [Fe(Htrz)₃](ClO₄)₂

Smit

Manoun

Waal

2001

J Raman Spectroscopy

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“…Unequivocal confirn~ation of these nitrogen frequencies ~ising isotopic substitution experiments has been obtained by Nakamoto and co-workers (14,15) who confirm the sequence, at least for 8-hydroxyq~iinoline derivatives (14). Further, the Ni-N stretching frequency in Ni(bip)l),.2Cl0,.2H2O has been unequivocally identified at 292cm-' (15).…”

Section: Introductionmentioning

confidence: 67%

Isotopic Studies of the Metal–Ligand Bond. Part III. The Far Infrared Spectra of Some Tetragonal Diamine Complexes of Cobalt(II) and Nickel(II): Studies of the Metal–Nitrogen Bond, as a Function of Metal Ion and of Spin State

Lever¹,

Mantovani²

1973

Can. J. Chem.

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The far infrared spectra of 35 complexes of the formula M(diamine),X, are reported where M = Co(I1) and Ni(II), X = C1-, Br-, I-, NO3-, SCN-, C104-, and AgIZ-and the diamine is ethylenediamine or its N,N-symmetric or antisymmetrically substituted dimethyl or diethyl derivative. Isotopic substitution studies with 62Ni and with are carried out with eleven characteristic complexes and assignments for the metal-nitrogen modes in both octahedral and square planar complexes so deduced. In most cases the appropriate number of metal-ligand modes, based on symmetry considerations, are observed. The variations in observed M-N frequencies are discussed in terms of the electronic and geometric factors previously utilized for the corresponding copper(I1) complexes. In complexes containing the asymmetric ligands, stretching vibrations arising from the two types of metal-nitrogen bond can be separately identified. Isotopic studies of pairs of complexes containing the same ligand and metal ion but with the latter in alternate spin states are reported here for the first time. All of the cobalt(I1) complexes and several of the nickel(I1) con~plexes are reported here for the first time.Les spectres dand l'infrarouge lointain de 35 complexes de formule M (diamine),X, ont etC rapportds, avec M = Co(I1) et Ni(II), X = C1-, Br-, I -, NO3-, SCN-, ClO4-, et Ag1,-et la diamine est 1'6th~-lenediamine ou ses derives N,N-dimethyles ou N,N-diethylis, symetriquement ou antisymetriquenlent substitues. Les etudes de substitution isotopique avec 62Ni et ,H ont etC effectuees sur onze complexes caracteristiques et les attributions sur les modes concernant la liaison metal-azote, a la fois pour les complexes octaedral et carre-plan, ont pu Ctre deduites. Dans la plupart des cas, le nombre approprie de modes relatifs au nlCta1-ligand bask sur des considerations de symetrie, a pu 6tre observe. Les variations dans les frequences M-N observees ont Cte discutees par rapport aux facteurs electroniques et gComCtriques precedemment utilises pour les complexes de cuivre(I1) correspondants. Dans les complexes comprenant des ligands asymktriques, les vibrations d'elongation qui sont dues aux deux types de liaison metal-azote ont pu 6tre separement identifiees. Les etudes isotopiques portant sur les paires de complexes contenant le mCme ligand et le mCme ion metal, ce dernier se trouvant dans des Ctats de spin alternes, ont etk rapportees ici pour la premiere fois. TOLE les complexes de cobalt(I1) et plusieurs complexes de nickel(I1) ont Bte decrits ici pour la premiere fois.[

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“…Moreover, v (CN) was not metal sensitive. So it was difficult to assign exact value to v (CN) , since several free 2, 2 / -bipyridine vibrations appeared in the same region 21,22 .…”

Section: Need For the Study (A)mentioning

confidence: 99%

NMR, ESR, NQR and IR Studies of Paramagnetic Macro Cyclic Complexes of 1st Transition Series Metal Ions Exhibiting MLCT Phenomenon: A DFT Application.Part: 1. [Bis (2, 2/-bi-pyridine)] Complexes

Sehgal¹,

Ahmad²

2017

Orient. J. Chem

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Metal isotope effect on metal-ligand vibrations. II. Tris complexes of 2,2'-bipyridine and 1,10-phenanthroline

Cited by 92 publications

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Low‐wavenumber Raman spectra of the spin‐transition complexes [Fe(NH₂ trz)₃](ClO₄)₂ and [Fe(Htrz)₃](ClO₄)₂

Low‐wavenumber Raman spectra of the spin‐transition complexes [Fe(NH₂ trz)₃](ClO₄)₂ and [Fe(Htrz)₃](ClO₄)₂

Isotopic Studies of the Metal–Ligand Bond. Part III. The Far Infrared Spectra of Some Tetragonal Diamine Complexes of Cobalt(II) and Nickel(II): Studies of the Metal–Nitrogen Bond, as a Function of Metal Ion and of Spin State

NMR, ESR, NQR and IR Studies of Paramagnetic Macro Cyclic Complexes of 1st Transition Series Metal Ions Exhibiting MLCT Phenomenon: A DFT Application.Part: 1. [Bis (2, 2/-bi-pyridine)] Complexes

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Metal isotope effect on metal-ligand vibrations. II. Tris complexes of 2,2'-bipyridine and 1,10-phenanthroline

Cited by 92 publications

References 0 publications

Low‐wavenumber Raman spectra of the spin‐transition complexes [Fe(NH2 trz)3](ClO4)2 and [Fe(Htrz)3](ClO4)2

Low‐wavenumber Raman spectra of the spin‐transition complexes [Fe(NH2 trz)3](ClO4)2 and [Fe(Htrz)3](ClO4)2

Isotopic Studies of the Metal–Ligand Bond. Part III. The Far Infrared Spectra of Some Tetragonal Diamine Complexes of Cobalt(II) and Nickel(II): Studies of the Metal–Nitrogen Bond, as a Function of Metal Ion and of Spin State

NMR, ESR, NQR and IR Studies of Paramagnetic Macro Cyclic Complexes of 1st Transition Series Metal Ions Exhibiting MLCT Phenomenon: A DFT Application.Part: 1. [Bis (2, 2/-bi-pyridine)] Complexes

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Low‐wavenumber Raman spectra of the spin‐transition complexes [Fe(NH₂ trz)₃](ClO₄)₂ and [Fe(Htrz)₃](ClO₄)₂

Low‐wavenumber Raman spectra of the spin‐transition complexes [Fe(NH₂ trz)₃](ClO₄)₂ and [Fe(Htrz)₃](ClO₄)₂