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1.
Begum N Hyder MI Kabir SE Hossain GM Nordlander E Rokhsana D Rosenberg E 《Inorganic chemistry》2005,44(26):9887-9894
Treatment of Mn(2)(CO)(10) with 3,4-toluenedithiol and 1,2-ethanedithiol in the presence of Me(3)NO.2H(2)O in CH(2)Cl(2) at room temperature afforded the dinuclear complexes Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (1), and Mn(2)(CO)(6)(mu-eta(4)-SCH(2)CH(2)S-SCH(2)CH(2)S) (2), respectively. Similar reactions of Re(2)(CO)(10) with 3,4-toluenedithiol, 1,2-benzenedithiol, and 1,2-ethanedithiol yielded the dirhenium complexes Re(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (3), Re(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S) (4), and Re(2)(CO)(6)(SCH(2)CH(2)S-SCH(2)CH(2)S) (5), respectively. In contrast, treatment of Mn(2)(CO)(10) with 1,3-propanedithiol afforded the trimanganese compound Mn(3)(CO)(6)(mu-eta(2)-SCH(2)CH(2)CH(2)S)(3) (6), whereas Re(2)(CO)(10) gave only intractable materials. The molecular structures of 1, 3, and 6 have been determined by single-crystal X-ray diffraction studies. The dimanganese and dirhenium carbonyl compounds 1-5contain a binucleating disulfide ligand, formed by interligand disulfide bond formation between two dithiolate ligands identical in structure to that of the previously reported dimanganese complex Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S). Complex 6, on the other hand, forms a unique example of a mixed-valence trimangenese carbonyl compound containing three bridging 1,3-propanedithiolate ligands. The solution properties of 6 have been investigated by UV-vis and EPR spectroscopies as well as electrochemical techniques. 相似文献
2.
W. Clark Still Lawrence J. Macpherson Toshiro Harada James F. Callahan Arnold L. Rheingold 《Tetrahedron》1984,40(12):2275-2281
The conformations of macrocyclic intermediates provide a useful medium through which distant chiral centers may control chemical reactions. In this paper, we show that macrocycles made by cyclization of simple acyclic starting materials with an auxiliary spacer may be used to prepare stereochemically complex acyclic products. 相似文献
3.
Various types of photometric titration curves are discussed. If a metal M is titrated conipleximetrically using a metal indicator and the absorbance is plotted vs. the titrant consumed, the inflection point appears at a pM value defined by the equation 3 pMinfl = pMtrans + 2 pMeqThis expression is valid when M combines in a 1 : 1 ratio with the complexing agent and the indicator and when the indicator concentration is small compared to the total metal concentration.The difference between the pM values at the inflection and equivalence points can be calculated from the equation ΔpM = pMinfl — pMeq = (pMtrans — pMeq) = log(CMK2MI/KMY)If the inflection point is taken as the equivalence point, the error arising can be calculated from ΔpM, or more simply, read from a diagram.If transmittance, instead of absorbancc, is plotted as a function of the titrant volume, the inflection point depends on the added amount of indicator. However, at high transmittance values, i.e., at low indicator concentrations, the inflection point of a transmittance curve occurs practically at the same volume of added titrant as the inflection point of an absorbance curve. Rules are given for applying an indicator correction for the amount of metal bound to the indicator at the end-point.The derived equations and discussions can also be applied to acid-base titrations. 相似文献
4.
Shariff?E.?KabirEmail author M.?Arzu?Miah M.?Abdur?Rahim Sonia?Sultana G.?M.?Golzar?Hossain Ebbe?Nordlander Edward?Rosenberg 《Journal of Cluster Science》2005,16(1):93-110
Treatment of Ru3(CO)12 with dpphSe2 (dpph = 1,6-bis(diphenylphosphino)hexane) in refluxing toluene in the presence of Me3NO afforded two new compounds, Ru3(CO)7(-CO)(3-Se)(-dpph) (1) and Ru3(CO)7(3-Se)2(-dpph) (2). A similar reaction of Ru3(CO)12 with dpppeSe2 (dpppe = 1,5-bis(diphenylphosphino)pentane) gave exclusively Ru3(CO)7(3-Se)2(-dpppe) (3). Treatment of Ru3(CO)12 with dpphS2 and dpppeS2 at 110°C in the presence of Me3NO afforded Ru3(CO)7(3-S)2(-dpph) (4) and Ru3(CO)7(3-S)2(-dpppe) (5), respectively. Reactions of Fe3(CO)12 with dpphSe2 and dpppeSe2, under identical conditions, afforded Fe3(CO)7(3-Se)2(-dpph) (6) and Fe3(CO)7(3-Se)2(-dpppe) (7), respectively. Compounds 1–7 were characterized spectroscopically and the molecular structures of compounds 1–4 were determined by single crystal X-ray crystallography. The core of 1 contains an equilateral triangle of ruthenium atoms with one capping selenium, one bridging dpph, one doubly bridging carbonyl and seven terminal carbonyl ligands. Complexes 2–4 have a square-pyramidal structure with two metal and two chalcogenide atoms alternating in the basal plane and the third metal atom at the apex of the pyramid, and belong to the family of well-known nido clusters with seven skeletal electron pairs. 相似文献
5.
A new method for searching internal coordinate conformational space systematically via a continuous-process procedure is described. Unlike previous systematic search methods, the new scheme generates torsionally remote conformers early in the search. It is also unbounded in that the extent of the search need not be specified at the outset. The search begins at low resolution (120° in torsion angle space) and then goes to higher and higher resolution as all points in space at a given resolution have been searched. The search may run without end or be terminated when new conformers cease to be found or when all space at some maximum allowable resolution has been explored. Conformational searches on several medium- and large-ring molecules using the new method are described and the results are compared with those from certain previously described search methods. It is found that the new method is significantly more efficient than previous procedures at finding all low energy conformers of organic molecules. 相似文献
6.
7.
Thapper A Behrens A Fryxelius J Johansson MH Prestopino F Czaun M Rehder D Nordlander E 《Dalton transactions (Cambridge, England : 2003)》2005,(21):3566-3571
Reaction of the tetradentate ligand N-(2-hydroxybenzyl)-N,N-bis(2-pyridylmethyl)amine (L-OH) with MoO2Cl2 in methanol in the presence of NaOMe and PF6- results in the formation of [MoO2(L-O)]PF6. Similarly, the reaction of N-(2-mercaptobenzyl)-N,N-bis(2-pyridylmethyl)amine (L-SH) with MoO2(acac)2 leads to the formation of [MoO2(L-S)]+. The dioxo-molybdenum complex [MoO2(L-O)]+ reacts with phosphines in methanol to afford phosphine oxides and an air-sensitive molybdenum complex, tentatively identified as [Mo(IV)O(L-O)(OCH3)]. The latter complex is capable of reducing biological oxygen donors such as DMSO or nitrate, thereby mimicking the activity of DMSO reductase and nitrate reductase. Reaction of [MoO2(L-O)]PF6 with PPh3 in other solvents than methanol leads to the formation of the Mo(V) dimer [(L-O)OMo(micro-O)MoO(L-O)](PF6)2. The crystal structures of [MoO2(L-O)]PF6 and the micro-oxo bridged dimer are presented. 相似文献
8.
In this paper we present an automated system for simultaneous measurement of CO(2) concentration, delta(13)C and delta(18)O from small (<1 mL) air samples in a short period of time (approximately 1 hour). This system combines continuous-flow isotope ratio mass spectrometry (CF-IRMS) and gas chromatography (GC) with an inlet system similar to conventional dual-inlet methods permitting several measurement cycles of standard and sample air. Analogous to the dual-inlet method, the precision of this system increases with the number of replicate cycles measured. The standard error of the mean for a measurement with this system is 0.7 ppm for the CO(2) concentration and 0.05 per thousand for the delta(13)C and delta(18)O with four replicate cycles and 0.4 ppm and 0.03 per thousand respectively with nine replicate cycles. The mean offset of our measurements from NOAA/CMDL analyzed air samples was 0.08 ppm for the CO(2) concentration, 0.01 per thousand for delta(13)C and 0.00 per thousand for delta(18)O. A specific list of the parts and operation of the system is detailed as well as some of the applications for micrometeorological and ecophysiological applications. 相似文献
9.
A series of aryl iodides, with a range of substituents, has been successfully coupled using 10 mol % Pd catalyst with samarium thiolates, derived from the corresponding aryl thiocyanates upon reductive cleavage with SmI(2). Reactions proceed in THF at 65 degrees C in yields ranging from good to excellent and are compatible with both electron-donating and electron-withdrawing substituents, except NO(2). The reactions may also be conducted with aryl bromides although with somewhat lower yields. 相似文献
10.
This investigation describes the reduction of an aryl thiocyanate with samarium(II) iodide, followed by reaction with various epoxides, to produce β-hydroxy sulfides. This method of ring opening of epoxides provides a substantial improvement in reaction time and convenience over existing methods while maintaining good regioselectivity and excellent yield. 相似文献