Mustafa Şenyel

Vibrational spectroscopic investigation and conformational analysis of 1-heptylamine: A comparative density functional study

FT-IR and Raman spectra of 1-heptylamine (1-ha) have been recorded in the region of 4000-10 cm(-1) and 4000-50 cm(-1), respectively. The conformational analysis, optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of 1-ha (C7H17N) have been examined by means of the Becke-3-Lee-Yang-Parr (B3LYP) density functional theory (DFT) method together with the 6-31++G(d,p) basis set. Furthermore, reliable vibrational assignments have been made on the basis of potential energy distribution (PED) and the thermodynamics functions, highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) of 1-ha have been predicted. Calculations have been carried out with the possible ten conformational isomers (TT, TG, GT, GT1, GG1, GG2, GG3, GG4, GG5, GG6; T and G denote trans and gauge) of 1-ha, both in gas phase and in solution. Solvent effects have theoretically been investigated using benzene and methanol. All results indicate that the B3LYP method provides satisfactory evidence for the prediction of vibrational frequencies and the TT isomer is the most stable form of 1-ha.

FT-IR and Raman spectroscopic and quantum chemical investigations of some metal halide complexes of 1-phenylpiperazine

New metal halide complexes in the form of M(pp)(2)Cl(2) (where pp=1-phenylpiperazine and M=Pd or Hg) have been prepared for the first time and their FT-IR and FT-Raman spectra are reported in the region of 4000-10 cm(-1) and 4000-50 cm(-1), respectively. The optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of the present compounds are theoretically examined by means of B3LYP hybrid density functional theory (DFT) method together with Lanl2dz basis set. Furthermore, reliable vibrational assignments made on the basis of potential energy distribution (PED) were calculated and the thermodynamics functions, the highest occupied and the lowest unoccupied molecular orbitals (HOMO and LUMO) of these compounds have been predicted. According to the results, theoretical values have been successfully compared against experimental data.

1H, 13C, 15N NMR and nJ(C, H) coupling constants investigation of 3-piperidino-propylamine: A combined experimental and theoretical study

Proton coupled and decoupled (13)C, (1)H, (15)N, DEPT, COSY, HETCOR and INADEQUATE NMR spectra of 3-piperidino-propylamine (3-pipa) have been reported for the first time. In order to provide a precise structural elucidation, the magnitude of (n)J(C, H) (n=1, 2, 3) coupling constants of 3-pipa (C(8)H(18)N(2)) have been determined. Solvent effects on chemical shifts have been investigated by using CDCl(3) and DMSO. Molecular mobility of the title molecule has also been investigated by performing (13)C NMR spin-lattice relaxation time (T(1)) measurements. (13)C, (1)H and (15)N NMR chemical shifts and (1-3)J(C, H) coupling constants of 3-pipa have been calculated by means of B3LYP density functional method with 6-311++G(d,p) basis set. Comparison between the experimental and the theoretical results indicates that density functional B3LYP method is able to provide satisfactory results for predicting NMR properties.

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.

An Infrared Spectroscopic Study on the Hofmann-diam-type 1,9-Diaminononanemetal(II) Tetracyanonickelate(II)-Aromatic Guest Clathrates: M(H2N(CH2)9NH2)Ni(CN)4 ċG(M = Cd or Ni; G = Benzene, Naphthalene, Anthracene or Phenanthrene

IR spectra of M(1,9-Diaminononane)Ni(CN)4ċG (M = Cd or Ni; G = benzene, naphthalene, anthracene or phenanthrene) are reported. The spectral data suggest that the host structures in these clathrates are similar to those of Hofmann-α, ω-diaminoalkane type clathrates.

4-Mercaptophenylboronic acid: Conformation, FT-IR, Raman, OH stretching and theoretical studies

4-Mercaptophenylboronic acid (4-mpba, C6H7BO2S) was investigated experimentally by vibrational spectroscopy. The molecular structure and spectroscopic parameters were studied by computational methods. The molecular dimer was investigated for intermolecular hydrogen bonding. Potential energy distribution analysis of normal modes was performed to identify characteristic frequencies. The present work provides a simple physical picture of the OH stretch vibrational spectra of 4-mpba and analogues of the compound studied. When the different computational methods are compared, there is a strong evidence of the better performance of the BLYP functional than the popular B3LYP functional to describe hydrogen bonding in the dimer. The findings of this research work should be useful to experimentalists in their quests for functionalised 4-mpba derivatives.

FT-IR Spectroscopic Study on Some 4-(3-Cyclohexen-1-yl)pyridine Metal(II) Tetracyanonickelate Complexes

New Hofmann-type complexes in the form of M(4-Chpy)2Ni(CN)4 [where 4-Chpy = 4-(3- cyclohexen-1-yl)pyridine and M = Ni, Co] were prepared in powder form, and their infrared spectra are reported in the range of 4000 - 400 cm−1. The spectral findings suggest that these compounds are similar in structure to the Hofmann-type complexes, and their structure consists of polymeric layers |M-Ni(CN)4|∞ with the 4-(3-cyclohexen-1-yl)pyridine molecule bound to the metal atom (M). PACS: 33.20.Ea, 33.20.Tp, 82.75-z

FT-IR spectroscopic study on some Hofmann-Td type complexes : Ni(4-Phenylpyridine)2M(CN)4 (M = Cd or Hg)

New Hofmann-Td type complexes in the form of Ni(4-Phenylpyridine)2M(CN)4 (M= Cd or Hg) were prepared in powder form and their infrared spectra are reported in the region of 4000 - 200 cm−1. From the spectral findings, these compounds are similar in structure to the Hofmann-Td type complexes.

Conformation and NH stretching of 1,1-dihalogenoheptan-1-amines [CH3(CH2)5CX2NH2; X = F, Cl or Br]: Halogen and solvent effects

The effects of halogen and solvent on the conformation and NH stretching of 1,1-dihalogeno-heptan-1-amines [CH3(CH2)5CX2NH2; X=F, Cl or Br] were investigated using the density functional theory method. The functional used was B3LYP employing the 6-31++G(d,p) basis set for all atoms. Computations were carried out for ten possible conformational isomers of the compounds, in the gas phase and both in a non-polar solvent (benzene) and in a polar solvent (methanol). This research work indicates that both the halogen and the medium affect conformational preference, geometrical parameters and NH vibrational frequency. The findings of this work can be useful to those systems involving changes in the conformations analogous to the compounds studied.