DFT study of the stereoselective formation of cis-W(CO)4(η2-C2H4)2 in the gas-phase consecutive coordination of C2H4 onto doubly coordinatively unsaturated W(CO)4.

B3LYP-based density functional theory (DFT) calculations are reported that provide insight into the stereoselective formation of cis-W(CO)(4)(η(2)-C(2)H(4))(2) observed in the pulsed 266 nm laser photolysis of tungsten hexacarbonyl (W(CO)(6)) in the presence of C(2)H(4) in the gas phase at room temperature (J. Phys. Chem. 1995, 99, 4558). W(CO)(4)(η(2)-C(2)H(4)) formed through the coordination of C(2)H(4) onto coordinatively unsaturated W(CO)(4) was found to have a pseudo-C(2v) symmetry (distorted trigonal bipyramid with an angle of ca. 90° between the two equatorial COs) with a bond dissociation enthalpy (BDE) of W-C(2)H(4) of 125 kJ mol(-1). In the subsequent coordination of C(2)H(4) onto the W(CO)(4)(η(2)-C(2)H(4)), having one vacant coordinatively unsaturated site, no barrier was found in the reaction path to cis-complex formation, while there was a barrier of about 89 kJ mol(-1) to the trans-complex. The calculations show that the stereoselective formation of cis-W(CO)(4)(η(2)-C(2)H(4))(2) is due to kinetic rather than thermodynamic control. The trans-W(CO)(4)(η(2)-C(2)H(4))(2) was calculated to be more stable than cis-W(CO)(4)(η(2)-C(2)H(4))(2) by about 10 kJ mol(-1). The BDE of W-C(2)H(4) in cis-W(CO)(4)(η(2)-C(2)H(4))(2) was estimated to be 61 kJ mol(-1).

[Outbreak of pulmonary tuberculosis in which tuberculosis developed from QuantiFERON-TB second generation (QFT-2G) test negative persons].

PURPOSE: To clarify the points to be considered when QFT-2G tests are used in the contacts examination by public health center. OBJECT & METHOD: We analyzed the results of contacts examination on 43 workplace colleagues (39 y/o and younger) of a pulmonary tuberculosis patient (bII2, Gaffky 9, cough for 1.5 months). RESULTS: After two months of the last contact with the index case, tuberculin skin tests, QFT-2G tests and chest X-rays were undertaken. After 6 months, chest X-rays were taken, and after 9 months, QFT-2G tests and chest CT scans were also undertaken. The tuberculin skin tests after two months showed a bimodal distribution, and 10 were QFT-2G positive and 2 showed doubtful reaction. The latter 12 persons underwent chemoprophylaxis. After 6 months, however, out of 31 QFT-2G negative persons, 2 developed pulmonary tuberculosis. Moreover, after 9 months, chest CT scans revealed 5 pulmonary tuberculosis patients. Three out of 7 new patients showed positive or doubtful reactions in QFT-2G tests undertaken after 9 months. DISCUSSION AND CONCLUSION: The sensitivity of QFT-2G tests is reported to be 80 to 90%, and the possibility of false negative is not negligible. We propose measures for public health center to conduct the contacts examination as follows; In case of high QFT-2G positive (including doubtful reaction) rate and/or a bimodal distribution of tuberculin skin test result, many infected persons are likely to be included in the group; and the following measures are recommended; 1) Necessity of chemoprophylaxis should be judged considering both tuberculin skin test results and the situation of contact with the index case, and not only by QFT-2G test results. 2) QFT-2G negative persons also need to be followed with chest X-rays.

Structure and infrared spectroscopy of group 6 transition-metal carbonyls in the gas phase: DFT studies on M(CO)n (M = Cr, Mo, and W; n = 6, 5, 4, and 3).

B3LYP-based density functional theory (DFT) calculations with effective core potentials (ECPs) (LANL2DZ) on M and 6-311+G(2d) all-electron basis function sets on C and O are used to interpret the symmetry characteristic vibrational absorption patterns of CO ligands in the "naked" coordinatively unsaturated transition-metal carbonyls M(CO)n-1 (M = Cr, Mo, and W; n = 4-6) observed by a time-resolved infrared absorption spectroscopy after the UV pulse laser photolysis of M(CO)6 in the gas phase. The UV photolysis results can be reasonably explained by the trends in the calculated bond dissociation enthalpies of M(CO)n-1-CO for group 6 metal carbonyls. M(CO)n-1 produced through one CO elimination from M(CO)n is found out to keep its parent skeleton, resulting in the structure with symmetry of C4v for M(CO)5, C2v for M(CO)4, and C3v for M(CO)3.