Six-coordinate organotin(IV) complexes formed using the Kläui ligands; [CpCo{P(OR′)2O}3]SnR3 − nCln

The complexes [CpCo{P(OR′)2O}3]SnR3 − nCln [R′ = Me, Et; R = Ph, Me] are readily prepared from the corresponding organotin chloride and the sodium salt of the Kläui ligands. The X-ray crystal structures of the full series are reported for R = Ph, n = 0-3, and these show that they are all six-coordinate, including the Ph3Sn derivative which is the first example of a SnC3O3 coordination sphere. 1H, 13C, 31P and 119Sn NMR spectra are reported, and interpreted in terms of significant second-order effects and fluxional processes

Case Report: Color as a Therapeutic Intervention

Peer reviewedFinal Accepted Versio

Sorption of sulfamethoxazole, sulfachloropyridazine and sulfamethazine onto six New Zealand dairy farm soils

We have investigated the sorption potential of three sulfonamides (SAs) in six New Zealand dairy farming soils using a modified batch equilibrium method employing 0.005 M CaCl₂ as background solution. Both liquid and solid phases were extracted to analyse for the antibiotic concentrations in order to avoid underestimation that may arise a result of photolysis or biotic degradation. The experimental data were later used to construct Freundlich isotherms to determine the effective distribution coefficients. Low log Koc value for all SAs suggests considerable leaching potential for SAs under conditions that are conducive for leaching. The sorption affinity for all soils followed the trend SCP>SMZ>SMO

Novel six-coordinate Aryl- and Alkyltin complexes

Organo-tin compounds have wide applications as pesticides and as intermediates for organic synthesis.¹ They are invariably Sn(IV) derivatives and are generally four-coordinate.² The mixed organo/chioro compounds of the type RnSnCI4-n do however have the ability to expand their coordination numbers to five or six. This depends critically on the substituents - with four organic groups, R₄Sn, there is no tendency at all to coordinate extra ligands, while at the other extreme SnCl₄ readily forms six-coordinate [SnC1₄L₂] complexes since the electronegative halo groups increase the Lewis acidity of the tin centre

Developing site-specific guidelines for orchard soils based on bioaccessibility – Can it be done?

Horticultural land within the periurban fringe of NZ towns and cities increasingly is being developed for residential subdivision. Recent surveys have shown that concentrations of As, Cd, Cu, Pb, and ΣDDT (sum of DDT and its degradation products DDE and DDD) in such soils can exceed criteria protective of human health.¹ Soil ingestion is a key exposure pathway for non-volatile contaminants in soil. Currently in NZ, site-specific risk assessments and the derivation of soil guidelines protective of human health assume that all of the contaminant present in the soil is available for uptake and absorption by the human gastrointestinal tract. This assumption can overestimate health risks and has implications for the remediation of contaminated sites.² In comparison, the bioavailability of contaminants is considered when estimating exposure via dermal absorption and by ingestion of home-grown produce.³ Dermal absorption factors and plant uptake factors are included in the calculations for estimating exposures via these routes

Inductive algebras and homogeneous shifts

Inductive algebras for the irreducible unitary representations of the universal cover of the group of unimodular two by two matrices are classified. The classification of homogeneous shift operators is obtained as a direct consequence. This gives a new approach to the results of Bagchi and Misra

The Interaction Among Multiple Governance Mechanisms at Young, Newly Public Firms

We focus on the relations among inside ownership, board composition, unaffiliated block ownership, and compensation structure for a sample of firms following their IPOs. Specifically, we follow firms for up to eleven years after their IPOs and examine the full sample and subsamples of firms that survive, are acquired, or that file for bankruptcy during the sample period. We find that as CEO ownership declines, board independence, board seats held by venture capitalists, and unaffiliated block ownership increase. Our findings suggest that as inside ownership decreases alternative governance mechanisms evolve to help mitigate the resulting increase in agency costs. Interestingly, the associations between CEO ownership, the fraction of venture capital board membership, and unaffiliated block ownership exist only for firms that survive over the eleven-year sample period

Platinum(II) phosphonate complexes derived from endo-8-camphanylphosphonic acid

The reactions of cis-[PtCl₂L₂] [L = PPh₃, PMe₂Ph or L₂ = Ph₂P(CH₂)₂PPh₂ (dppe)] with endo-8-camphanylphosphonic acid (CamPO₃H₂) and Ag₂O in refluxing dichloromethane gave platinum(II) phosphonate complexes [Pt(O₃PCam)L₂]. The X-ray crystal structure of [Pt(O₃PCam)(PPh₃)₂]•₂CHCl₃ shows that the bulky camphanyl group, rather than being directed away from the platinum, is instead directed into a pocket formed by the Pt and the two PPh₃ ligands. This allows the O₃P–CH₂ group to have a preferred staggered conformation. The complexes were studied in detail by NMR spectroscopy, which demonstrates non-fluxional behaviour for the sterically bulky PPh₃ and dppe derivatives, which contain inequivalent phosphine ligands in their ³¹P NMR spectra. These findings are backed up by theoretical calculations on the PPh₃ and PPhMe₂ derivatives, which show, respectively, high and low energy barriers to rotation of the camphanyl group in the PPh₃ and PPhMe₂ complexes. The X-ray crystal structure of CamPO₃H₂ is also reported, and consists of hydrogen-bonded hexameric aggregates, which assemble to form a columnar structure containing hydrophilic phosphonic acid channels surrounded by a sheath of bulky, hydrophobic camphanyl groups