Hypercoordinated organotin compounds containing sulfur and chlorine. Molcular structures of [(Ph3P)2N]+[S(SnR2Cl)2Cl]- (R=Me, t-Bu)

The reaction of diorganotin sulfides, cyclo-(R₂SnS)_n (R=Me, n-Bu; n=3; R=t-Bu; n=2) with the corresponding diorganotin dichlorides, R₂SnCl₂, provided the tetraorganodistannathianes, (R₂ClSn)₂S (1, R=Me; 2, R=n-Bu; 3, R=t-Bu). ¹H-, ¹³C-, and ¹¹⁹Sn-NMR studies indicate that these compounds are kinetically labile and in equilibrium with the starting materials. Addition of equimolar amounts of [(Ph₃P)₂N]Cl to the reaction mixtures gave the chloride complexes [(Ph₃P)₂N]⁺[S(SnR₂Cl)₂Cl]⁻ (4, R=Me; 5, R=n-Bu; 6, R=t-Bu). Single-crystal X-ray diffraction studies revealed the tin atoms in both 4 and 6 to adopt distorted trigonal bipyramidal configurations with the chlorine atoms occupying the axial positions.

Chiral trialkoxysilanols derived from terpene alcohols. Molecular structures of tris([(1S)-endo]-(-)-bornoxy)silanol and tetrakis((-)-menthoxy)silane

Terpene alcohols (−)-menthol and [(1S)-endo]-(−)-borneol react with SiCl₄ in the presence of base to give (MenO)₃SiCl (1) and (BorO)₃SiCl (2) in high yields. Hydrolysis of 1 yields (MenO)₃SiOH (4) and (MenO)₄Si (3). Hydrolysis of 2 yields only (BorO)₃SiOH (5). The crystal structures of 3 and 5 are reported.

Synthesis and reactivity towards DIBAL-H of Cyclo-Siloxanes cyclo-[R2SiOSi(Ot-Bu)2O]2, cyclo-(t-BuO)2Si(OSiR2)2O, and cyclo-R2Si[Osi(Ot-Bu)2]2O (R=Me, Ph)

The six-, eight- and twelve-membered cyclo-siloxanes, cyclo-[R₂SiOSi(Ot-Bu)₂O]₂ (R = Me (1), Ph (2)), cyclo-(t-BuO)₂Si(OSiR₂)₂O (R = Me (3), Ph (4)), cyclo-R₂Si[OSi(Ot-Bu)₂]₂O (R = Me (5), Ph (6)) and cyclo-[(t-BuO)₂Si(OSiMe₂)₂O]₂ (3a) were synthesized in high yields by the reaction of (t-BuO)₂Si(OH)₂ and [(t-BuO)₂SiOH]₂O with R₂SiCl₂ and (R₂SiCl)₂O (R = Me, Ph). Compounds 1 - 6 were characterized by solution and solid-state ²⁹Si NMR spectroscopy, electrospray mass spectrometry and osmometric molecular weight determination. The molecular structure of 4 has been determined by single crystal X-ray diffraction and features a six-membered cyclo-siloxane ring that is essentially planar. The reduction of 1 - 6 with i-Bu₂AlH (DIBAL-H) led to the formation of the metastable aluminosiloxane (t-BuO)₂Si(OAli-Bu₂)₂ (7) along with Me₂SiH₂ and Ph₂SiH₂.

Single enatiomer free-radical chemistry - Lewis acid-mediated reductions of racemic halides using chiral non-racemic stannanes

Additions of one to two equivalents of Lewis acids that include magnesium salts to free-radical reduction reactions involving ester functionalized radicals and (1R,2S,5R)-menthyldiphenyltin hydride 4, bis((1R,2S,5R)-menthyl)phenyltin hydride 5, tris((1R,2S,5R)-menthyl)tin hydride 6, bis((1R,2S,5R)-menthyl)-[8-(N,N-dimethylamino)naphthyl]tin hydride 12, bis((1R,2S,5R)-menthyl)-[1-((S)-N,N-dimethylaminoethyl)phenyl]tin hydride 13 or 3α-dimethylstannyl-5α-cholestane 14 result in remarkable enantioselectivities. Examples include (S)-naproxen ethyl ester 16, produced in 74% yield and greater than 99% ee at −78°C from the bromide and 5 in the presence of MgBr₂, and ethyl (R)-N-trifluoroacetyl-_D-phenylglycinate 18, obtained in 78% yield and 99% ee under identical conditions. Kinetic and computational studies provide insight into the origins of these observations.

Hydrolysis of dinuclear spacer-bridged diorganotin(IV) triflates. A novel cationic double ladder with supramolecular association

A series of oligomethylene-bridged diorganotin triflates R(OTf)₂Sn(CH₂)_nSn(OTf)₂R (R = CH₂SiMe₃; n = 3, 4, 8, 10) were synthesized by reaction of triflic acid with the precursor oxides R(O)Sn(CH₂)_nSn(O)R. On the basis of ¹¹⁹Sn NMR (in acetonitrile) the triflates appear to be the simple six-coordinated ionic species [(MeCN)₄(RSn(CH₂)_nSnR)(MeCN)₄]²⁺. These triflates readily undergo hydrolysis to give products, the identity of which depends on the length of the oligomethylene bridge. For n = 3 (5), the solid-state structure shows association of two dimeric units, which results in a tetracationic double ladder. Extensive hydrogen bonding gives rise to a supramolecular association. Solution ¹¹⁹Sn NMR and ES MS suggest some dissociation of 5 into dimers containing four tin atoms and possibly monomers containing two tin atoms. A rudimentary solid-state structure for n = 4 (6) indicates a linear polymer based on dimeric (four tin atoms) units. The structure of 6 also features extensive hydrogen bonding, this time effectively giving rise to alternating layers of cations and anions.

Spatial prediction of rufous bristlebird habitat in a coastal heathland: a GIS-based approach

1. To develop a conservation management plan for a species, knowledge of its distribution and spatial arrangement of preferred habitat is essential. This is a difficult task, especially when the species of concern is in low   abundance. In south-western Victoria, Australia, populations of the rare rufous bristlebird Dasyornis broadbenti are threatened by fragmentation of suitable habitat. In order to improve the conservation status of this species, critical habitat requirements must be identified and a system of corridors must be established to link known populations. A predictive spatial model of rufous bristlebird habitat was developed in order to identify critical areas requiring preservation, such as corridors for dispersal.
2. Habitat models generated using generalized linear modelling techniques can assist in delineating the specific habitat requirements of a species. Coupled with geographic information system (GIS) technology, these models can be extrapolated to produce maps displaying the spatial configuration of suitable habitat.
3. Models were generated using logistic regression, with bristlebird presence or absence as the dependent variable and landscape variables, extracted from both GIS data layers and multispectral digital imagery, as the predictors. A multimodel inference approach based on Akaike’s information criterion was used and the resulting model was applied in a GIS to extrapolate predicted likelihood of occurrence across the entire area of concern. The predictive performance of the selected model was evaluated using the receiver operating characteristic (ROC) technique. A hierarchical partitioning protocol was used to identify the predictor variables most likely to influence variation in the dependent variable. Probability of species presence was used as an index of habitat suitability.
4. Negative associations between rufous bristlebird presence and  increasing elevation, 'distance to cree', 'distance to coast' and sun index were evident, suggesting a preference for areas relatively low in altitude, in close proximity to the coastal fringe and drainage lines, and receiving less direct sunlight. A positive association with increasing habitat complexity also suggested that this species prefers areas containing high vertical density of vegetation.
5. The predictive performance of the selected model was shown to be high (area under the curve 0·97), indicating a good fit of the model to the data. Hierarchical partitioning analysis showed that all the variables considered had significant  independent contributions towards explaining the variation in the dependent variable. The proportion of the total study area that was predicted as suitable habitat for the rufous bristlebird (using probability of occurrence at a ≥0·5 level ) was 16%.
6. Synthesis and applications. The spatial model clearly delineated areas predicted as highly suitable rufous bristlebird habitat, with evidence of potential corridors linking coastal and inland populations via gullies. Conservation of this species will depend on management actions that protect the critical habitats identified in the model. A multi-scale  approach to the modelling process is recommended whereby a spatially explicit model is first generated using landscape variables extracted from a GIS, and a second model at site level is developed using fine-scale habitat variables measured on the ground. Where there are constraints on the time and cost involved in measuring finer scale variables, the first step alone can be used for conservation planning.

Ontogeny of diving behaviour in the Australian sea lion: trials of adolescence in a late bloomer

1.Foraging behaviours of the Australian sea lion (Neophoca cinerea) reflect an animal working hard to exploit benthic habitats. Lactating females demonstrate almost continuous diving, maximize bottom time, exhibit elevated field metabolism and frequently exceed their calculated aerobic dive limit. Given that larger animals have disproportionately greater diving capabilities, we wanted to examine how pups and juveniles forage successfully.
2.Time/depth recorders were deployed on pups, juveniles and adult females at Seal Bay Conservation Park, Kangaroo Island, South Australia. Ten different mother/pup pairs were equipped at three stages of development (6, 15 and 23 months) to record the diving behaviours of 51 (nine instruments failed) animals.
3. Dive depth and duration increased with age. However, development was slow. At 6 months, pups demonstrated minimal diving activity and the mean depth for 23-month-old juveniles was only 44 ± 4 m, or 62% of adult mean depth.
4. Although pups and juveniles did not reach adult depths or durations, dive records for young sea lions indicate benthic diving with mean bottom times (2·0 ± 0·2 min) similar to those of females (2·1 ± 0·2 min). This was accomplished by spending higher proportions of each dive and total time at sea on or near the bottom than adults. Immature sea lions also spent a higher percentage of time at sea diving.
5. Juveniles may have to work harder because they are weaned before reaching full diving capability. For benthic foragers, reduced diving ability limits available foraging habitat. Furthermore, as juveniles appear to operate close to their physiological maximum, they would have a difficult time increasing foraging effort in response to reductions in prey. Although benthic prey are less influenced by seasonal fluctuations and oceanographic perturbations than epipelagic prey, demersal fishery trawls may impact juvenile survival by disrupting habitat and removing larger size classes of prey. These issues may be an important factor as to why the Australian sea lion population is currently at risk.

Distribution of an alien aquatic snail in relation to flow variability, human activities and water quality

1. Disturbance and anthropogenic land use changes are usually considered to be key factors facilitating biological invasions. However, specific comparisons of invasion success between sites affected to different degrees by these factors are rare.

2. In this study we related the large-scale distribution of the invading New Zealand mud snail (Potamopyrgus antipodarum) in southern Victorian streams, Australia, to anthropogenic land use, flow variability, water quality and distance from the site to the sea along the stream channel.

3. The presence of P. antipodarum was positively related to an index of flow-driven disturbance, the coefficient of variability of mean daily flows for the year prior to the study.

4. Furthermore, we found that the invader was more likely to occur at sites with multiple land uses in the catchment, in the forms of grazing, forestry and anthropogenic developments (e.g. towns and dams), compared with sites with low-impact activities in the catchment. However, this relationship was confounded by a higher likelihood of finding this snail in lowland sites close to the sea.

5. We conclude that P. antipodarum could potentially be found worldwide at sites with similar ecological characteristics. We hypothesise that its success as an invader may be related to an ability to quickly re-colonise denuded areas and that population abundances may respond to increased food resources. Disturbances could facilitate this invader by creating spaces for colonisation (e.g. a possible consequence of floods) or changing resource levels (e.g. increased nutrient levels in streams with intense human land use in their catchments).

Australian sentencing : principles and practice

Australian Sentencing: Principles and Practice explains the rules, principles, policies and practices that underpin the manner in which people are punished for criminal behaviour in Australia. As well as dealing with sentencing law today, the book provides an extensive analysis of the wider policy, moral, and political consideration which shape sentencing law. It analyses and evaluates existing standards and practices, and suggests how sentencing law should be reformed so that it operates in a fairer, more efficient and effective manner.

Content: Part A: 1. The nature of sentencing and theories of punishment; 2. Plucking figures from the air: the instinctive synthesis; 3. The objectives that are attainable through sentencing; 4. High Court sentencing jurisprudence; Part B: 5. The principle of proportionality; 6. Aggravating factors; 7. Mitigating considerations; 8. The relevance of a guilty plea to sentence; 9. The relevance of prior criminality; 10. Aboriginality; Part C: 11. The nature of criminal sanctions; 12. Imprisonment; 13. Intermediate sanctions; 14. Discharges and bonds, fines and disqualifications; Part D: 15. The way forward ? strategic sentencing.

Ontogeny of oxygen stores and physiological diving capability in Australian sea lions

1.For air-breathing animals in aquatic environments, foraging behaviours are often constrained by physiological capability. The development of oxygen stores and the rate at which these stores are used determine juvenile diving and foraging potential.
2. We examined the ontogeny of dive physiology in the threatened Australian sea lion Neophoca cinerea. Australian sea lions exploit benthic habitats; adult females demonstrate high field metabolic rates (FMR), maximize time spent near the benthos, and regularly exceed their calculated aerobic dive limit (cADL). Given larger animals have disproportionately greater diving capabilities; we wanted to determine the extent physiological development constrained diving and foraging in young sea lions.
3. Ten different mother/pup pairs were measured at three developmental stages (6, 15 and 23 months) at Seal Bay Conservation Park, Kangaroo Island, South Australia. Hematocrit (Hct), haemoglobin (Hb) and plasma volume were analyzed to calculate blood O2 stores and myoglobin was measured to determine muscle O₂. Additionally, FMR's for nine of the juveniles were derived from doubly-labelled water measurements.
4. Australian sea lions have the slowest documented O₂ store development among diving mammals. Although weaning typically occurs by 17·6 months, 23-month juveniles had only developed 68% of adult blood O₂. Muscle O₂ was the slowest to develop and was 60% of adult values at 23 months.
5. We divided available O₂ stores (37·11 ± 1·49 mL O₂ kg−1) by at-sea FMR (15·78 ± 1·29 mL O₂ min−1 kg−1) to determine a cADL of 2·33 ± 0·24 min for juvenile Australian sea lions. Like adults, young sea lions regularly exceeded cADL's with 67·8 ± 2·8% of dives over theoretical limits and a mean dive duration to cADL ratio of 1·23 ± 0·10.
6. Both dive depth and duration appear impacted by the slow development of oxygen stores. For species that operate close to, or indeed above their estimated physiological maximum, the capacity to increase dive depth, duration or foraging effort would be limited. Due to reduced access to benthic habitat and restricted behavioural options, young benthic foragers, such as Australian sea lions, would be particularly vulnerable to resource limitation.

The relative importance of landscape properties for woodland birds in agricultural environments

1. Studies of landscape change are seldom conducted at scales commensurate with the processes they purport to investigate. Landscape change is a landscape-level process, yet most studies focus on patches. Even when landscape context is considered, inference remains at the patch-level. The unit of investigation must be extended beyond individual patches to whole mosaics in order to advance understanding of faunal responses to landscape change.

2. In this study, we aggregated data from multiple sites per landscape such that both the response and explanatory variables characterized 'whole' landscapes, allowing for landscape-level inference about factors influencing species' incidence.

3. We used hierarchical partitioning and Bayesian variable selection methods to develop species-specific models that examined the influence of four categories of landscape properties – habitat extent, habitat configuration, landscape composition and geographical location – on the incidence of 58 species of woodland-dependent birds in 24 agricultural landscapes (each 100 km2) in south-eastern Australia.

4. There was strong evidence for a positive effect of habitat extent for 27 species. Thirty species were related to at least one of the four landscape composition variables, and geographical location was important for 19 species. Habitat configuration was influential for 13 species and where important, the impacts of fragmentation per se were detrimental.

5. Variation among species in the influential landscape variables indicates that different species respond to different sets of cues in land mosaics. Thus, although all species were grouped a priori as 'woodland-dependent', expectations based on general ecological characteristics may prove unreliable.

6. Synthesis and applications. These results underscore the value of moving beyond the fragmentation paradigm focused on the spatial pattern of habitat vs. non-habitat, to a greater appreciation of the composition and heterogeneity of land mosaics. Landscape-level inference will enable improved conservation outcomes by recognizing the influence of landscape properties on biota and devising strategies at this scale to complement patch-based management. We provide strong empirical evidence that biodiversity management in agricultural landscapes must focus on habitat extent. Complementary management of other landscape attributes, such as habitat aggregation and intensity of agricultural land-use, will also enhance the value of agricultural landscapes for woodland birds.

Auditor independence: regulation, oversight and inspection

Much of what auditors do is unobservable. Indeed, what goes on in an audit has been described as ‘secret audit business’. Audits in this context are of financial reports and those financial reports are the representations of the management of those companies, not the auditors. The audits of financial reports are of value in that they provide a competent and independent (of auditee management) attestation of the validity of those management representations. This attestation lowers the ‘information risk’ for the users of these financial reports. There has been a marked increase in activity to regulate matters relating to independence. The proposals outlined in CLERP 9 are one example of this. The requirements in the United States under the Sarbanes-Oxley Act are a further example.

Audit firms operate in a highly regulated yet highly competitive market. Evidence exists to suggest that audit firms are active competitors in respect of audit pricing and competency, including specialist industry expertise. Until recently, there has been little or no observable evidence that audit firms compete in respect of independence. The issues as they relate to audit independence are complex. One issue is that threats to independence are frequently subtle and difficult to observe and measure. Hence, controlling the decisions that relate to them cannot rely solely on regulation which itself inevitably relies on crude definitions and imprecise measures. Additionally, further regulation may not achieve the desired end without other processes being but in place in tandem.

This paper argues that:

1. auditors of certain classes of companies (in particular, those that are publicly traded) should be provided with incentives or requirements to have observable processes on independence
2. the means of observability should be in the form of an inspection and review process focussing on issues critical to the audit, such as independence
3. expert persons not having a current or past financial interest in the firm or in the commercial outcomes of the review should be used in the inspection and review process
4. the review process should have wide-ranging powers of inspection to examine the policies, processes, structures and ‘culture’ of audit firms
5. the report of the inspection and review should be made public, unedited and in full, and in a timely fashion. The primary objectives of this proposal are to (1) make more transparent to the market for information the characteristics of the audit firms and their process to ensure audit independence, and (2) provide a rigorous oversight of independence decision-making by persons who have no commercial interest in the outcome of the decision.

Comparison of the flexibility of eight-membered tetrasiloxane and stannasiloxane rings: a crystallographic and computational study

The syntheses and crystal structures of the eight-membered cyclo-stannasiloxanes cyclo-[t-Bu(OH)Si(OSnt-Bu₂O)₂Si(OH)t-Bu] (1) and cyclo-{t-Bu₂Si[OSn(CH₂SiMe₃)₂O]₂Sit-Bu₂} (2) as well as the synthesis of the six-membered cyclo-stannasiloxane cyclo-{t-Bu₂Si[OSn(CH₂SiMe₃)₂]₂O} (3) are reported. Compound 1 crystallizes as its trans isomer, but the cis isomer dominates in solution. In agreement with the experimentally obtained results, ab initio and DFT calculations on the model compounds cyclo-(H₂SiO)₄ (4), cyclo-[H₂Si(OSnH₂)OSiH₂] (5), cyclo-O(H₂SiOSnH₂)₂O (6), and cyclo-[H₂Si(OSiH₂)OSnH₂] (7) indicate that the energetic preference to adopt puckered structures increases and the ring flexibility decreases with an increasing number of tin atoms in the ring. The rich diversity of puckered conformations is attributed to the steric demand of the different organic substituents.

New insights in asymmetric tetraorganodistannoxane ladder formation. A NMR-spectroscopic and crystallographic study

The syntheses of the asymmetrically substituted tetraorganodistannoxanes [t-Bu₂(X)SnOSn(Y)(CH₂SiMe₃)₂1₂ (1, X = Y = OH; 2, X = Cl, Y = OH; 3, X = Y = Cl) are reported and their structures in solution and in the solid state are characterized by multinuclear NMR spectroscopy and single crystal X-ray analyses. In toluene, the tetrahydroxy-substituted derivative 1 is in equilibrium with the organotin oxides cyclo-[t-Bu₂Sn{OSn(CH₂SiMe₃)₂}₂O] (4), cyclo[(Me₃SiCH₂)₂Sn(OSnt-Bu₂)₂O] (5), and cyclo-(t-Bu₂SnO)₃, and some additional, undefined species containing pentacoordinated tin atoms. In contrast, the dihydroxydichloro-substituted derivative 2 is inert in solution.

Hydrolysis of bis((trimethylsilyl)methyl)tin dihalides. Crystallographic and spectroscopic study of the hydrolysis pathway

The synthesis and characterization by multinuclear NMR spectroscopy of the diorganotin dihalides (Me₃SiCH₂)₂SnX₂ (1, X = Cl; 2, X = Br), the diorganotin dichloride water adduct (Me₃SiCH₂)₂SnCl₂·H₂O (1a), the dimeric tetraorganodistannoxanes [(Me₃SiCH₂)₂(X)SnOSn(Y)(CH₂SiMe₃)₂]₂ (3, X = Y = Cl; 4, X = Br, Y = OH; 5, X = Br, Y = F; 6, X = Y = OH; 8, X = Cl, Y = OH), and the molecular diorganotin oxide cyclo-[(Me₃SiCH₂)₂SnO]₃ (7) are reported. The structures in the solid state of compounds 1a, 3, 6, and 7 were determined by single-crystal X-ray analysis. In toluene solution, the hydroxy-substituted tetraorganodistannoxane 6 is in equilibrium with the diorganotin oxide 7 and water. The eight-membered diorganotin oxide cyclo-[(Me₃SiCH₂)₂SnO]₄ (7a) is proposed to be involved in this equilibrium. On the basis of the results of this and previous works, a general hydrolysis pathway is developed for diorganotin dichlorides containing reasonably bulky substituents.