A photoelectron spectroscopic and theoretical study of the halogen and hydrogen thiocyanates and isothiocyanates

Leung, Henry; Suffolk, R. J.; Watts, John D. W.

doi:10.1016/0301-0104(86)87059-8

Cited by 23 publications

(21 citation statements)

References 63 publications

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“…Some non-metalsubstituted SCN such as halogen-and hydrogenthiocyanates and isothiocyanates (Howell, Absar & Van Waze, 1973;Leung, Suffolk & Watts, 1986) (5) 131 (3) 101 (3) cyclopropyl isothiocyanate (Durig, Sullivan, Berry & Cradock, 1987), methyl-and cyano-derivatives (Barone, Cristinziano, Lelj & Russo, 1982) were analysed using ab initio calculations. Electronic molecular properties of thiocyanate and the metal-anion pair were analysed only for Li (Musaev, Yakobson & Charkin, 1989;Parrini & Morales, 1993;Squalli, Costa, Cartier & Chabanel, 1994) and Cu (Musaev, Makhaev & Charkin, 1991).…”

Section: Scn Internal Geometrymentioning

confidence: 99%

Statistical Analysis of Noncovalent Interactions of Anion Groups in Crystal Structures. III. Metal Complexes of Thiocyanate and their Hydrogen-Donor Accepting Function

Tchertanov¹,

Pascard²

1997

Acta Crystallogr Sect B

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The bidentate function of the thiocyanate anion was studied using the Cambridge Structural Database System. Complexing properties (metal-thiocyanate interactions) with respect to metal cations were analysed. Two main classes were distinguished: (a) alkali and alkaline earth metals, and (b) metals of Zn and Cu groups and transition metals (group VIII). Good correlations were found between the nature of the metal (radius, oxidation state and charge) and its position relative to the thiocyanate unit. Hydrogen-bond acceptor properties of discrete and complexed SCN units were compared. The extraordinarily active hydrogenbonding behaviour allows this anion to act as a powerful bridge between different molecular fragments. In metal complexes the cation provokes a redistribution of anionic charge in SCN and the distribution of electron density, in turn, controls the hydrogen-bonding properties of the terminal acceptor atom. Binding properties of thiocyanate in biological systems were illustrated using the Brookhaven Protein Data Bank. A comparison of anion binding in small-molecule structures and in macromolecular structures shows good agreement.

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Section: Scn Internal Geometrymentioning

confidence: 99%

Statistical Analysis of Noncovalent Interactions of Anion Groups in Crystal Structures. III. Metal Complexes of Thiocyanate and their Hydrogen-Donor Accepting Function

Tchertanov¹,

Pascard²

1997

Acta Crystallogr Sect B

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“…The first theoretical studies were reviewed by Hargittai & Paul (1977) and recently developed by ab initio molecular orbital (MO) calculations (Parrini & Morales, 1993). Experimental data, however, were obtained only by microwave, IR and photoelectron spectroscopy (Leung, Suffolk & Watts, 1986) in the gas phase.…”

Section: Introductionmentioning

confidence: 99%

Statistical analysis of noncovalent interactions of anion groups in crystal structures. II. Hydrogen bonding of thiocyanate anions

Tchertanov¹,

Pascard²

1996

Acta Crystallogr Sect B

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The hydrogen-bond acceptor function of the thiocyanate anion is analyzed in 52 crystal structures retrieved from the Cambridge Crystallographic Database. All modes of hydrogen-bond coordination are represented: by the sulfur, by the nitrogen and by the zr-system of the anion. The preferred areas for the H donors (D=OH and NH groups) were determined: (a) around sulfur, as a torus centered at the S end, the axis of which is the linear anion, and with an average DSN angle of 99 °, and (b) around nitrogen, on a spherical cap delimited by the solid angle, SND (average= 145°), with the linear anion. The anion-acceptor function is characterized by multiple hydrogen bonding and, in most cases (80%), thiocyanate binds through both acceptor centers (S and N). Important backbonding of sulfur in the thiocyanate anion is structurally evidenced.

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“…[18,[25][26][27] However, this trend is reversed in ONSCN, as is the case in ONNCO. [13] Because of the extensive incorporation of the π NO antibonding character into the 18aЈ, with π nb (aЈ) character, its ionization becomes less energetic.…”

Section: Photoelectron Spectroscopymentioning

confidence: 45%

“…[13] Because of the extensive incorporation of the π NO antibonding character into the 18aЈ, with π nb (aЈ) character, its ionization becomes less energetic. Compared with analogous molecules XSCN (X = CH 3 , Cl, Br, I) [18,26,27] the separation of π nb (aЈ) and π nb (aЈЈ) is also quite narrow. The obvious decrease of the separation of nonbonding π orbitals (π nb ) in cis-1a reflects the direct interaction between the π SCN and π NO moieties.…”

Section: Photoelectron Spectroscopymentioning

confidence: 95%

“…The shape and intensity of the first group of bands suggest that it should be attributed to two ionization processes. Consistent with analogous molecules XSCN (X = H [25] , CH 3 [26] , Cl [18] , Br [18] , I [27] ), the first two bands are assigned to the nonbonding in-and out-of-plane π orbitals [π nb (aЈ) and π nb (aЈЈ)] partially localized on the pseudohalide group. In the molecule ONNCO [13] , the first two orbitals π nb (aЈ) and π nb (aЈЈ) are distributed fairly evenly over the whole molecule, whereas for cis-1a there is a dominant S 3p involvement in the first two π orbitals as indicated by the two relatively low ionization potentials.…”

Section: Photoelectron Spectroscopymentioning

confidence: 96%

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First Experimental Observation of Gas‐Phase Nitrosyl Thiocyanate

Yao

Zeng

et al. 2006

Eur J Inorg Chem

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The unstable nitrosyl thiocyanate molecule has been generated in the gas phase for the first time from an in situ heterogeneous reaction at low temperature. The product was detected and characterized by a photoelectron spectrometerphotoionization mass spectrometer (PES-PIMS). The electronic and geometric structures of the molecule were investigated with the help of quantum chemical calculations at the

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A photoelectron spectroscopic and theoretical study of the halogen and hydrogen thiocyanates and isothiocyanates

Cited by 23 publications

References 63 publications

Statistical Analysis of Noncovalent Interactions of Anion Groups in Crystal Structures. III. Metal Complexes of Thiocyanate and their Hydrogen-Donor Accepting Function

Statistical Analysis of Noncovalent Interactions of Anion Groups in Crystal Structures. III. Metal Complexes of Thiocyanate and their Hydrogen-Donor Accepting Function

Statistical analysis of noncovalent interactions of anion groups in crystal structures. II. Hydrogen bonding of thiocyanate anions

First Experimental Observation of Gas‐Phase Nitrosyl Thiocyanate

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