Sulfoxide as a ligand in iron(II) porphyrinates: S- or O-bound?

In order to study the bonding of sulfoxides to iron(II) porphyrinates, an equilibrium study of Fe(TPP) with tetramethylenesulfoxide (TMSO) has been performed. UV-vis spectra at different concentrations of TMSO have shown distinct character belonging to three species: four-coordinate Fe(II)(TPP), five-coordinate [Fe(II)(TPP)(TMSO)], and six-coordinate [Fe(II)(TPP)(TMSO)2]. The isosbestic points for the low TMSO concentrations suggest that the equilibrium constant K1 is much larger than K2. Analysis of spectral data by the nonlinear least-squares program SQUAD gives K1 = 267 and K2 approximately 1. Even though the five-coordinate species is the dominant species under the synthetic conditions, only the six-coordinate species was crystallized and characterized by an X-ray diffraction study. [Fe(TPP)(TMSO)2] (C52H44Fe-N4O2S2): monoclinic, P2(1)/c, a = 11.2580(3) A, b = 15.9262(5) A, c = 12.3930(4) A, beta = 116.246(1) degrees , V = 1992.95(10) A3, Z = 2. X-ray crystallography demonstrates the complex is a low-spin bis-TMSO ligated species. The average Fe-Np distance is 1.999(4) A. The most important feature is that TMSO is coordinated to iron(II) by the sulfur donors, not oxygen. The Fe-S distance is 2.2220(3) A.     

Addition of H2 Across a Cobalt–Phosphorus Bond

Addition of H₂ across the cobalt–phosphorus bond of (PPP)CoPMe₃ ( 3 ) is demonstrated, where PPP is a monoanionic diphosphine pincer ligand with a central N‐heterocyclic phosphido (NHP^?) donor. The chlorophosphine Co^II complex (PP^ClP)CoCl₂ ( 2 ) can be generated through coordination of the chlorophosphine ligand (PP^ClP, 1 ) to CoCl₂. Subsequent reduction of 2 with KC₈ in the presence of PMe₃ generates (PPP)CoPMe₃ ( 3 ), in which both the phosphorus and cobalt centers have been reduced. The addition of 1 atm of H₂ to complex 3 cleanly affords (PP^HP)Co(H)PMe₃ ( 4 ), in which H₂ has ultimately been added across the metal–phosphorus bond. Complex 4 was characterized spectroscopically and using computational methods to predict its geometry.     

MS3 using the collision cell of a tandem mass spectrometer system

We report the feasibility of multistage fragmentation in combination with a fast background subtraction method, yielding the equivalent of MS3. The first quadrupole selects an ion of interest, and the ion is axially accelerated into Q2 to generate fragment ions. Subsequent stages of mass selection and fragmentation are obtained by quadrupolar resonant excitation within the Q2 collision cell. The fragments are analyzed downstream by either a resolving quadrupole or a time-of-flight (TOF) mass spectrometer, and multistage spectra are obtained by subtraction (MS(n) - MS(n-1)) for n = 3 or 4. We discuss the characterization of this method, including product ion arrival times, fragmentation efficiencies, and ion selectivity. We report accurate TOF mass spectra of background-subtracted MS3 for protonated molecules reserpine (m/z 609), bosentan (m/z 1552), and taxol (m/z 854).     

Simplification and analysis of a model of social interaction in voting

A recently proposed model of social interaction in voting is investigated by simplifyingit down into a version that is more analytically tractable and which allows a mathematicalanalysis to be performed. This analysis clarifies the interplay of the different elementspresent in the system – social influence, heterogeneity and noise – and leads to a betterunderstanding of its properties. The origin of a regime of bistability is identified. Theinsight gained in this way gives further intuition into the behaviour of the originalmodel.     

Theoretical and experimental 1H, 13C and 15N NMR studies of N‐alkylation of substituted tetrazolo[1,5‐a]pyridines

The ¹⁵N as well as ¹H and ¹³C chemical shifts of nine substituted tetrazolopyridines and their corresponding tetrazolopyridinium salts have been determined by using NMR spectroscopy at the natural abundance level of all nuclei in CD₃CN. In this paper, we report, for the first time, the N‐alkylation reaction of electron deficient tetrazolopyridines. The treatment of tetrazolopyridines 5–13 with one equivalent of trialkyloxonium tetrafluoroborate leads to a mixture of two isomers, i.e. N3‐ and N2‐alkyl tetrazolo[1,5‐a]pyridinium salts. It has been observed that the N3‐isomer is always the major isomer, except in the case of the CF₃ substituent, where the two isomers are obtained in the same amount. The quaternary tetrazolopyridinium nitrogen N3 is shielded by around 100 ppm (parts per million) with respect to the parent tetrazolopyridine. Experimental data are interpreted by means of density functional theory (DFT) calculations, including solvent‐induced effects, within the conductor‐like polarizable continuum model (CPCM). Good agreements between theoretical and experimental ¹H, ¹³C and ¹⁵N NMR were found. The combination of multinuclear magnetic resonance spectroscopy with gauge including atomic orbital (GIAO) DFT calculations is a powerful tool in the structural elucidation for both neutral and cationic heterocycles and in the determination of the orientation of N‐alkylation of tetrazolopyridines. Copyright © 2009 John Wiley & Sons, Ltd.     

A re-determination of the standard potential of the Pb2+ (aq)|Pb(s) half cell

The standard reduction potential of the Pb²⁺ (aq)|Pb(s) half-cell at 298 K has been re-determined and found to be ? 126.7 ± 0.2 mV, 0.4 mV more negative than the currently accepted value. The new value is used to calculate a self-consistent set of solubility products for several sparingly soluble lead salts using the known E⁰s of the appropriate lead-lead salt electrodes. Activity. Activity coefficients of lead chloride in aqueous solution are also given.     

Cluster chemistry: XXXIX. Gold—ruthenium clusters with sulphur ligands: Synthesis and structure of HRu3Au(μ3-S)(CO)9(PPh3), Ru3Au(μ3-SBut)(CO)9(PPh3) and Ru3Au2(μ3-S)(CO)9(PPh3)2

H₂Ru₃(μ₃-S)(CO)₉ is deprotonated by K[HBBu^s₃] to give cluster anions which react with [O{Au(PPh₃)}₃]⁺ or with AuCl(PPh₃)/T1⁺ to give HRu₃Au(μ₃-S)(CO)₉(PPh₃) (1) and Ru₃Au₂(μ₃-S)(CO)₉(PPh₃)₂ (3). A similar sequence with HRu₃(μ₃-SBu^t)(CO)₉ leads to Ru₃Au(μ₃-SBu^t)(CO)₉(PPh₃) (2) as the main product although some 1 also forms, indicating SC cleavage competes with deprotonation of HRu₃(μ₃-SBu^t)(CO)₉ by [HBBu^s₃]^?. The X-ray crystal structures of 1, 2 and 3 are described; (1) and (2) have “butterfly” AuRu₃ cores with markedly different hinge angles of 119 and 148° respectively, while 3 has a trigonal-bipyramidal Au₂Ru₃ skeleton. All three clusters have the sulphur atom symmetrically bridging the Ru₃ triangular face.