Ab initio molecular orbital theory has been used to study the formation and reactions of the sulfursulfur hemibonded dimer radical cation of thiirane. Two fragmentation pathways, hemibond cleavage and ethylene extrusion, leading to the fragmentation of this species have been examined. The barriers to these processes are found to be similar and moderately large (127 and 160 kJ mol-', respectivel...

SB-3CT is a 2-[(arylsulfonyl)methyl]thiirane that achieves potent inhibition, by a thiirane-opening mechanism, of the MMP2 and MMP9 zinc metalloproteases. The deprotonation mechanism for thiirane opening of SB-3CT and for the opening of its oxirane analogue, both relevant to the inhibition of MMP2, was investigated computationally using the acetate anion as the Brønsted base and in methanol and...

Adiabatic ionization energies of dimethyl sulfide (DMS) and ethylene sulfide (thiirane) are both accurately and precisely determined to be 8.6903 +/- 0.0009 and 9.0600 +/- 0.0009 eV, respectively, by vacuum-UV mass-analyzed threshold ionization (MATI) spectroscopy. Also reported are vibrational frequencies of DMS and thiirane monocations. Simulations using a Franck-Condon analysis based on ab i...

The mechanism of inhibition of estrogen synthetase (P-450arom) by 19R- and 19S-isomers of 10-oxiranyl-and 10-thiiranyl-4-estrene-3,17-dione was investigated using human placental microsomes and purified enzyme preparations. The 19R-isomers were potent inhibitors and exhibited affinities 36-fold (10-oxirane) and 80-fold (10-thiirane) greater than the respective 19S-isomers. Kinetic experiments s...

The rotational spectrum of an//-2,3-dimethylthiirane, CH 3 -C 2 H 2 S-CH 3 , was recently investigated in our laboratory [1]. In this study the rotational spectra of the normal, 3 S, and l 3 C isotopomers were measured, assigned and analysed for internal rotation and the molecular structure. The present communication aims at the nuclear quadrupole coupling of the 3 S isotopomer, measured in nat...

The reaction of Mn(2)(CO)(7)(mu-S(2)) with [CpNi(CO)](2) yielded the paramagnetic new compound Cp(2)Ni(2)Mn(CO)(3)(mu(3)-S)(2) (1) and a new hexanuclear metal product Cp(2)Ni(2)Mn(4)(CO)(14)(mu(6)-S(2))(mu(3)-S)(2) (2). Structurally, compound 1 contains two triply bridging sulfido ligands on opposite sides of an open Ni(2)Mn triangular cluster. EPR and temperature-dependent magnetic susceptibil...

The halogen bond in the thiirane···ClF complex is shown to be unusually strong using high-accuracy ab initio methods. Investigating the underlying mechanism of the interaction reveals a significant increase in charge transfer and suggests it should be labelled as a Mulliken inner complex.

Reaction of thiodiacetate anion (tda) with [Cu(TMEDA)(NO3)2] (TMEDA = N,N,N'N'-tetramethyl ethylene-diamine) in a stoichiometric ratio afforded the complex {[Cu(TMEDA)(tda)]·(H2TMEDA)(NO3)2·H2O} (1). When [Cu(TMEDA)(NO3)2] was added in excess, it yielded a μ-oxalato complex {[Cu2(TMEDA)2(μ-ox)(H2O)2](NO3)2·2CH3CN} (2). The reaction involves a facile room temperature desulfurization of the thiod...

Reanalysis of the 3 S Hyperfine Structure in the Rotational Spectrum of Thiirane Barbara Kirchner , Hanspeter Huber , Gero ld Steinebrunner, Helmut Dreizler , Jens-Uwe G r a b o w 3 , and I lona M e r k e b Institut für Physikalische Chemie der Universität Basel, Klingelbergstr. 80, CH-4056 Basel a Institut für Physikalische Chemie der Christian-Albrechts-Universität zu Kiel, Olshausenstr. 40, ...