T. W. Swaddle

Bio: T. W. Swaddle is an academic researcher from University of Calgary. The author has contributed to research in topic(s): Raman spectroscopy & Diethylenetriamine. The author has an hindex of 2, co-authored 3 publication(s) receiving 51 citation(s).

Vibrational spectra of some isonitrile complexes of cobalt(I) and (II)

Abstract: The Raman and low-frequency infrared spectra of the trigonal-bipyramidal complexes Co(RNC)5ClO4(R = Me, Et, Ph) have been recorded and assigned. It is found that δ(CoCN) modes occur at higher frequencies than ν(Co—CN) modes. Although Raman spectra of the blue and yellow forms of Co(PhNC)5(ClO4)2 could not be obtained, the low-frequency infrared spectra are consistent with the C4v structure previously suggested (1). The dimeric complexes Co2(RNC)10(ClO4)4 (R = Me, Et) have been studied, and tentative assignments of the Raman and infrared spectra made on the basis of D4d symmetry. Spectra of the complexes Co2(RNC)10I(ClO4)3 (R = Me, Et) strongly support the previously suggested structural formulation (2) [(MeNC)5Co—I—Co(MeNC)5](ClO4)3, and furthermore indicate that the Co—I—Co skeleton is linear.

The vibrational spectra of simple cobalt(III) and chromium(III) ammine complexes

Abstract: Laser Raman spectral data are presented for solid [Co(NH3)6]X3 (where X = Cl, Br and I), [Co(NH3)5Cl]Cl2, cis- and trans-[Co(NH3)4Cl2]Cl, and the sulfate and pentachlororocuprate (II) of Cr(NH3)63+, together with Raman spectra of aqueous solutions of Co(NH3)63+ and Co(NH3)5Cl2+ salts. Difficulties in obtaining Raman spectra of some Cr(NH3)63+salts are exlained in terms of photochemical reactions. The assignments of the metal-ligand vibrational spectra of these complexes are discussed; previous controversy has arisen through the occurrence of Raman-active bands in the infrared spectrum. The A1g cobalt-ammine stretching vibration appears twice in the Raman spectra of solid hexaamminecobalt(III) chloride and bromide, because of low crystal lattice symmetry.

Far infrared and Raman spectra of the pentachlorocuprate(II) anion

Abstract: The far i.r. and Raman spectra of the compounds [Co(NH3)6][CuCl5], [Cr(NH3)6][CuCl5], and (dienH3)[CuCl5](dien = diethylenetriamine), have been recorded. The spectra of the anions have been assigned on the basis of a D3h environment of the copper(II) ion.

Transition Metal-lsocyanide Complexes

Abstract: Publisher Summary This chapter discusses the field of transition-metal complexes of isocyanides developed slowly over more than a century to a respectable subarea in coordination chemistry and which, in the process, seems to have attracted very little attention. The valence-bond pictures for an isocyanide and carbon monoxide and for metal complexes of these ligands emphasize the similarities of both the ligands and their complexes. The insertion of a carbonyl group into a metal–alkyl or metal–aryl bond and the reverse reaction involving decarbonylation of an acyl complex have been studied from both the synthetic and mechanistic points of view. The reactions of nucleophilic reagents with cationic and uncharged metal carbonyl complexes have received much attention in the past, and it is not surprising that these studies have now been extended to isocyanide metal complexes. Perhaps the greatest excitement in the field of metal isocyanide complex chemistry has been generated by the observation that a variety of protonic substances (alcohols, thiols, amines, and hydrazine) add to the coordinated isocyanide ligand. A number of chemists have been interested in the chemistry of cobinamine and cobaloxime complexes of several ligands, including isocyanides.

Preparation of tetrakis(t-butylisocyanide)aquacobalt(II) perchlorate and reaction with tertiary phosphine ligands

Abstract: Reaction of t-butylisocyanide with Co(ClO4)2· 6H2O in 4:1 molar ratio in EtOH at O °C produces [Co(CNCMe3)4H2O](ClO4)2 in near quantitative yields. Ligand substitution/reduction reactions of [Co(CNCMe3)4H2O] (ClO4)2 (in CH3CN) with triarylphosphines (in CH2Cl2) at 25 °C are rapid and in good yield;[Co(CNCMe3)3{P(C6H4OMe-p)3}2]ClO4, [Co(CNCMe3)3{P(C6H4Cl-p)3}2]ClO4, and [Co(CNCMe3)3{P(C6H5)3}2]ClO4 were prepared. Analogous reaction with As(C6H5)3 caused intense color change, but only unsubstituted [Co(CNCMe3)4H2O](ClO4)2 was recovered. Reaction of [Co(CNCMe3)4H2O](ClO4)2 with trialkylphosphines produced [Co(CNCMe3)3{P(C6H13-n)3}2] ClO4, [Co(CNCMe3)3{P(CH2CH2CN)3}2] ClO4, and [Co(CNCMe3)3{P(NMe2)3}2]ClO4, but anticipated monosubstituted product with P(NEt2)3 was not recovered. Infrared, 1H NMR and electronic spectra give some indication of coordination structure.