Trends in metal-biradical exchange interaction for first-row M(II)(nitronyl nitroxide-semiquinone) complexes

We report molecular structures and temperature-dependent magnetic susceptibility data for several new metal complexes of heterospin triplet ground-state biradical ligands. The ligands are comprised of both nitronyl-nitroxide (NN) and semiquinone (SQ) spin carriers. Five compounds are five-coordinate M(II) complexes (M = Mn, Co, Ni, Cu, and Zn), and one is a six-coordinate Ni(II) complex. Five compounds were structurally characterized. During copper complex formation a reaction with methanol occurs to form a unique methoxy-substituted SQ ring. Variable-temperature magnetic susceptibility studies are consistent with strong intraligand (NN-SQ and NN-PhSQ) ferromagnetic exchange coupling. For the five-coordinate Mn, Co, and Ni complexes, the S = 1 ligand is antiferromagnetically coupled to the metal. For both the five-coordinate Cu complex and the six-coordinate Ni complex, the ligand is ferromagnetically coupled to the metal spins in accordance with orbital symmetry arguments. Despite the low molecular symmetries, the predicted trend in metal-ligand exchange interactions is supported by spin dimer analysis based on extended Hückel calculations. For (NN-SQ)NiTp(Cum,Me)() (Tp(Cum,Me)() = hydro-tris(3-cumenyl-5-methylpyrazolyl)borate), an antisymmetric exchange term was required for the best fit of the magnetic susceptibility data. Antisymmetric exchange was less important for the other complexes due to inherently smaller Deltag. Finally, it is shown that intraligand exchange coupling is of paramount importance in stabilizing high-spin states of mixed metal-biradical complexes.     

A stable silicon congener of highly strained bicyclo[3.2.0]hepta-1,3,6-triene

A silicon-containing fused bicyclic compound with a highly strained bridgehead double bond, 2,3,6,7-tetra-tert-butyl-4-(tert-butyldimethylsilyl)-5-(tert-butyldimethylsiloxy)-5-silabicyclo[3.2.0]hepta-1,3,6-triene (2), was synthesized quantitatively by the reaction of 1,2-bis-tert-butyl-4,4-bis(tert-butyldimethylsilyl)-4-silatriafulvene (3) with di-tert-butylcyclopropenone (4) at 80 degrees C. An X-ray crystallographic analysis for 2 not only confirmed a bicyclic structure having a silacyclopentadiene (silole) ring fused with a silacyclobutene ring but also the remarkable deformation around the double bonds; the sum of the bond angles around the unsaturated bridgehead carbon was 333 degrees . The strain energy of a model 5-silabicyclo[3.2.0]hepta-1,3,6-triene was calculated at the MP2/6-31+G(d,p)//B3LYP/6-31+G(d) level (30.2 kcal/mol) to be comparable to that for parent bicyclo[3.2.0]hepta-1,3,6-triene (30.7 kcal/mol). Despite the high steric strain, 2 was stable enough to be kept intact for several months in the air. The high stability is ascribed to the effective steric protection of the ring system by the bulky substituents.     

Radical ions : XXVI. Radical anions of perphenylcyclopolysilanes

Perphenylcyclopolysilanes [Si(C₆H₅)₂]_n (n = 4, 5) are reduced by potassium to radical anions. Their simple ESR spectra demonstrate, that the extra electron is confined to the inner Si_nC_2n skeleton of the uncleaved and presumably planarized cyclopolysilanes.     

Determination of total tin in silicate rocks by graphite furnace atomic absorption spectrometry

A method is described for the determination of total tin in silicate rocks utilizing a graphite furnace atomic absorption spectrometer with a stabilized-temperature platform furnace and Zeeman-effect background correction. The sample is decomposed by lithium metaborate fusion (3 + 1) in graphite crucibles with the melt being dissolved in 7.5% hydrochloric acid. Tin extractions (4 + 1 or 8 + 1) are executed on portions of the acid solutions using a 4% solution of trioctylphosphine oxide in methyl isobutyl ketone (MIBK). Ascorbic acid is added as a reducing agent prior to extraction. A solution of diammonium hydrogenphosphate and magnesium nitrate is used as a matrix modifier in the graphite furnace determination. The limit of detection is > 10 pg, equivalent to > 1 μg l^?1 of tin in the MIBK solution or 0.2–0.3 μg g^?1 in the rock. The concentration range is linear between 2.5 and 500 μg l^?1 tin in solution. The precision, measured as relative standard deviation, is < 20% at the 2.5 μg l^?1 level and < 7% at the 10–30 μg l^?1 level of tin. Excellent agreement with recommended literature values was found when the method was applied to the international silicate rock standards BCR-1, PCC-1, GSP-1, AGV-1, STM-1, JGb-1 and Mica-Fe. Application was made to the determination of tin in geological core samples with total tin concentrations of the order of 1 μg g^?1 or less.     

The role of palladium catalyst and base in stereoselective transformations of (E)-2-chlorovinylsulfides

Stereoselective transformations of 2-chlorovinylsulfides in the presence of soluble (t-BuOK) or insoluble (solid KOH or Cs₂CO₃/18-crown-6) base and palladium catalyst (dppb)Pd(OAc)₂ have been studied. Depending on the substrate or catalytic system, the reaction leads to the formation of (E)-1,2-bis[aryl(or arylmethyl)thio]ethenes and/or (E)-1,4-bis[aryl(or arylmethyl)thio]-1-buten-3-ynes in yields of up to 93%.     

A New Synthetic Route to Unsymmetrical 1,2-Bis(phosphanyl)ethanes and 1,2-Arsanyl(phosphanyl)ethanes with and without a Stereogenic Center

A one-pot reaction affords unsymmetrical 1,2-bis(phosphanyl)ethanes 2 and 1,2-arsanyl(phosphanyl)ethanes 3 from the cyclic sulfate 1 in high yield. Similarly, chiral 1,2-bis(phosphanyl)ethanes and 1,3-bis(phosphanyl)propanes could be obtained in enantiomerically pure form. R, R'=alkyl, phenyl.     

Determination of optimal variable-sized multiple-block appointment systems

The single-block appointment system is the most common method of scheduling ambulatory care clinics today. Several studies have examined various appointment systems ranging from single-block appointments on one extreme to individual appointments on the other, and including mixtures of these such as multiple-block (m-at-a-time) and block/individual systems. In this paper we analyze a general single-server multiple-block system, one permitting blocks of variable size. In the analysis we use a dynamic programming approach, with some modifications to compensate for the non-Markov nature of the problem. Analytical results and approximations which significantly reduce the computational requirements for a solution are obtained. Examples demonstrate that under certain weightings of the criteria of waiting, idle, and overtime, the generality of the system considered here allows performance superior to that of other commonly used systems.