Ziya Kantarci

Structure and vibrational spectroscopy of methanesulfonic acid hydrazide: an experimental and theoretical study

A comprehensive study of the molecule of methanesulfonic acid hydrazide (MSH) is presented. The X-ray structure shows that in the crystal two centrosymmetrically oriented MSH molecules are held together by N–H···N hydrogen bonding interactions. This feature is unprecedented for the known arylsulfonic hydrazide analogues. The energetics of the various MSH staggered conformers and the stabilisation due to dimerisation are evaluated by HF abinitio calculations. Moreover, the pathways that interconvert the conformers as well as their enantiomers are outlined. The transition states between conformers correspond to the eclipsed conformation about the S–N linkage while those between enantiomers require planarisation of the N atom bound to sulfur. Some interconversions require two steps and two barriers to be bypassed. The IR and Raman spectra of MSH have been recorded and a normal coordinate analysis (NCA) has been carried out. The assignments have been double-checked through the abinitio calculated frequencies. The latter techniques also allow evaluation of the normal modes of vibration due to interacting MSH monomers, which can be experimentally detected.

An infrared and raman spectroscopic study of pyrazinecadmium (II) tetracyanometalate (II) Benzene (1/1) clathrates: Cd(C4H4N2)Cd(CN)4⁗C6H6 and Cd(C4H4N2)Hg(CN)4⁗C6H6

Two new benzene clathrates of the form Cd(Pyrazine)M(CN)4⁗C6H6, where M = Cd or Hg, have been prepared and their infrared and Raman spectra are reported.

VIBRATIONAL SPECTROSCOPIC STUDIES ON THE EN-TD-TYPE BENZENE CLATHRATES : M(ETHYLENEDIAMINE)M'(CN)4.2C6H6 (M=MN OR CD, M'=CD OR HG)

IR spectra of Mn(en)M(CN)4·2C6H6 (M=Cd or Hg), and IR and Raman spectra of Cd(en)M(CN)4·2C6H6 (M=Cd or Hg) clathrates are reported. The spectral features suggest that the first two compounds are similar in structure to the later two Td-type clathrates.

An infrared and Raman spectroscopic study of Td-type 4,4′-bipyridylcadmium(II) tetracyanometallate (II) benzene (1/2) clathrates: Cd(C10H8N2)Cd(CN)4 · 2C6H6 and Cd(C10H8N2)Hg(CN)4 · 2C6H6

Two new benzene clathrates of the form Cd(4,4′-bipyridyl)M(CN)4 · 2C6H6, (M=Cd or Hg) have been prepared in powder form. Their spectral data were compared with those of the corresponding host complexes and found to be consistent with the host structure found in Td-type clathrates.

Structure and Conformation of 4,4′-Bipyridine

Abstract The title compound has been investigated by x-ray analysis and AM1 semi-empirical quantum mechanical method. The geometry of the two molecules in the asymmetric unit is different in terms of the torsion angle θ [C4-C5-C6-C10] between the two pryidne rings which is -34.1 (2)° and -17.9 (2)° in molecule I and II respectively. The conformation of the energy profile showed that the minimum energy conformation has the torsion angle θ near 35°. The crystal structure is stabilized by C-H … N hydrogen bonds.

An infrared spectroscopic study on Hofmann-type complexes of dimethyl sulfoxide

Abstract The infrared spectra of M(DMSO) 2 NI(CN) 4 (M = Mn, Co, Fe, Cu; DMSO = dimethyl sulfoxide) and M(DMSO)(py)Ni(CN) 4 , (M = Mn, Ni; py = pyridine) complexes are reported. In all the complexes, the SO stretch is shifted to a lower frequency than in the free molecule, indicating coordination through oxygen. Several modes of the pyridine in the M(DMSO)(py) Ni(CN) 4 complexes have upward shifts in frequency compared to those in the free molecule, indicating that the molecule does not act as a guest molecule in the M(DMSO) 2 Ni(CN) 4 host lattice, but is bonded directly to the metal (M) together with dimethyl sulfoxide.

Vibrational spectroscopic studies on the hofmann-Td-type clathrates: M(NH3)2M′(CN)4·2C6H6 (M=Mn or Cd and M′=Cd or Hg0

IR spectra of Mn(NH3)2M(CN)4·2C6H6 (M=Cd or Hg), and IR and Raman spectra of Cd(NH3)2M(CN)4·2C6H6 (M=Cd or Hg) are reported. The spectral data suggest that the former two compounds are similar in structure to the latter two Td-type clathrates.

Vibrational spectra of dipyridine-1-oxide metal (II) tetracyanonickelate complexes

Abstract Six new Hofmann-type complexes. M(pyridine-1-oxide)2(Ni(CN)4(M is Mn, Fe, Co, Ni, Cu, and Cd), have been prepared and their infrared and Raman spectra are reported. Effects of metal-ligand bond formation on the vibrational modes of pyridine-1-oxide are examined.

An Infrared Spectroscopic Study on the Hofmann-diam-type 1,12-Diaminododecanemetal(II) Tetracyanonickelate(II)-aromatic Guest Clathrates: M(H2N(CH2)12NH2)Ni(CN)4ċG(M=Co, Ni or Cd; G = Benzene, Naphthalene, Anthracene, Phenanthrene or Biphenyl)

Three Hofmann-diaminododecane-type clathrates of the form M(1,12-diaminododecane) Ni(CN)4ċG (M = Co, Ni or Cd; G = benzene, naphthalene, anthracene, phenanthrene or biphenyl) have been prepared in powder form. The 1,12-diaminododecane molecules in the host lattice permit the inclusion of bulky guest molecules. The spectral features suggest that these compounds are similar in structure to the other Hofmann-diam-type clathrates.

Infrared Spectroscopic and Gravimetric Studies on the Dicyclohexylaminecadmium(II) Tetracyanopalladate(II) Host-Aromatic Guest Systems

The host complex Cd(Cyclohexylamine)2Pd(CN)4 has been prepared in powder form. The spectral data suggest that the structure of this complex issimilar to those of the Hofmann-dma-type hosts. The sorption processes of thearomatic guests (benzene, toluene,o-, m-, p-xylene, naphthalene, 1,2-, 1,3-, 1,4-dichlorobenzene and 1,4-dibromobenzene) in this host have been examined at room temperature by gravimetric and spectroscopic measurements.The desorption of the benzene guest against time has been measured. The hoststructure changes on inclusion of the guests and recovers after liberations. Thehost complex has been suggested as sorbents for selective absorption.