Synthesis, characterization and DFT studies of the cobalt(III) complex of a tetrapodal pentadentate N4S donor ligand

The synthesis of the pentadentate ligand 2,6-bis(3,3-dimethyl-2,4-dioxocyclohexanyl)-4-thiaheptane (N(4)Samp) is described. The synthetic pathway involves the coupling of two 1,3-(dimethylenedioxy)-2-methyl-2-(methylene-p-toluenesulfonyl)propane moieties with sodium sulfide and subsequent synthetic elaboration to prepare the final N4S donor system. The cobalt(III) complex [Co(N(4)Samp)Cl](2+) has been prepared and subsequently crystallized as the tetrachlorozincate salt. The X-ray structure analysis confirms the pentadentate nature of the ligand and shows the thioether donor occupying one apex with four equivalent amine donors effectively occupying the equatorial plane of the molecule. The sixth coordination site is occupied by a chloro ligand. The electronic absorption and C-13 NMR spectra have been studied. DFT calculations have been employed to explore structural and mechanistic comparisons between [Co(N(4)Samp)Cl](2+) and an analogous pentaamine complex.

Cattle, crops and clearing: Regional drivers of landscape change in the Brigalow Belt, Queensland, Australia, 1840-2004

Landscape change occurs through the interaction of a multitude of natural and human driving forces at a range of organisational levels, with humans playing an increasingly dominant role in many regions of the world. Building on the current knowledge of the underlying drivers of landscape change, a conceptual framework of regional landscape change was developed which integrated population, economic and cultural values, policy and science/technology. Using the Southern Brigalow Belt biogeographic region of Queensland as a case study, the role of natural and human drivers in landscape change was investigated in four phases of settlement since 1840. The Brigalow Belt has experienced comparable rates of vegetation clearance over the past 50 years to areas of tropical deforestation. Economic factors were important during all phases of development, but the five regional drivers often acted in synergy. Environmental constraints played a significant role in slowing rates of change. Temporal trends of deforestation followed a sigmoidal curve, with initial slow change accelerating though the middle phases then slowing in recent times. Future landscape management needs to take account of the influence of all the components of the conceptual framework, at a range of organisational levels, if more ecologically sustainable outcomes are to be achieved. (c) 2006 Elsevier B.V. All rights reserved.