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The family of N,N-dimethylaminomethylferrocene compounds is one of the most important in ferrocene chemistry. They serve as precursors for a range of anti-malarial and anti-tumour medicinal compounds, in addition to being key precursors for ferrocene ligands in the Lucite alpha process. A brief discussion on the importance and synthesis of N,N-dimethylaminomethyl-substituted ferrocenes preludes the synthesis of the new ligand, 1,1′,2,2′-tetrakis-(N,N-dimethylaminomethyl)ferrocene. The crystal structure of this compound is reported, and a comparison is made with its disubstituted analogue, 1,2-bis-(N,N-dimethylaminomethyl)ferrocene. The tetrahedral nickel dichloride complexes of both these ligands have been crystallographically characterised. Finally, a pointer to future research in the area is given, which includes a discussion of a new method to extract ferrocenylmethylamines from mixtures using additives and a new synthetic avenue from substituted cyclopentadiene itself.

In this paper, the clean high yielding, synthesis, and structure of the tetraphosphine ligand, 1,1′,2,2′-tetrakis-(di-isopropyl-phosphino)ferrocene, (tdipf), is described. In addition, improved synthesis methods for 1,1′,2,2′-tetrakis(diphenylphosphino)ferrocene, (tppf), and 2,2′-bis-(diphenylphosphino)-1,1′-dibromoferrocene are also reported, and the synthetic method is generalised to include the synthesis of 3,3′-bis-(diphenylphosphino)-1,1′,2,2′-tetrabromoferrocene. The related ligands 2,2′-bis-(iso-propylphosphino)-1,1′-bis-diphenylphosphinoferrocene (diprdppf) and 2,2′-bis-(di-isopropylphosphino)-dibromoferrocene have also been prepared and characterised. The crystal structure of the square planar bimetallic nickel (II) dichloride of tdipf is also described, together with a brief NMR study investigating the synthesis of this and related metal complexes. The crystal structures of the palladium and platinum dichloride complexes of 2,2′-bis-(di-isopropylphosphino)-1,1′-dibromoferrocene, bpdbf, are also discussed in the context of comparison with previously known crystal structures in the same general family. A general discussion on the synthetic methodology is given, along with indications for future research that other researchers might explore.

The reaction of the bulky ligand 1,2-bis-(di-tert-butylphosphinomethyl)benzene, 1 with [Ni(DME)Cl2], 3, DME = 1,2-dimethoxyethane, at room temperature over extended periods, affords the new blue Zwitterionic complex [2-(C6H4-CH2P(H)tBu2-1-(CH2PtBu2NiCl3)], 4, which contains a phosphonium group and an anionic nickel trichloride. This complex decomposes in alcohols such as methanol and the solution turns yellow. A discussion of the possible mechanism leading to the observed product is presented. Key to this is identification of the source of the phosphonium proton, which we speculated to arise from trace water in the initial nickel complex. To prove that trace water was present in [Ni(DME)Cl2], a sample of this precursor was reacted under similar condition with anhydrous DMF alone. In addition to the known complex [Ni(DMF)6)]2+[NiCl4]2−, 5, we identified the trans-diaqua complex [Ni(Cl)2(H2O)2(DMF)2], 6, which proved the presence of trace water. Interestingly in dimethylformamide, [2-(C6H4-CH2P(H)tBu2-1-(CH2PtBu2NiCl3)] exhibits thermochromic properties: an solution that is pale blue at ambient temperature reversibly changes colour to yellow upon cooling. This behaviour is specific to DMF and is related to the solvato-chromic behaviour exhibited by related DMF–nickel complexes. A discussion of the NMR spectra of compound 4 in a range of solvents is presented. The structures of the previously prepared molybdenum complex, [1,2-(C6H4-CH2PtBu2)2Mo(CO)4] and the bis-(phosphine sulphide) of the ligand, [1,2-(C6H4-H2P(S)tBu2)2], 5, are described for structural comparative purposes.

A series of nickel (II) bis-phosphine organometallic complexes along with two pseudo [M7] (M = Ni(II), Zn(II)) metallocalix[6]arene complexes and a dysprosium acetate coordination polymer have each been crystallised in the presence of localized magnetic fields set up using neodymium magnets, using custom made Magnetic Crystallization Towers (MCTs). In all cases, whether the product complex is diamagnetic or paramagnetic, a complex spatial patterning of the crystals occurs based on the orientation of the magnetic field lines. When using magnetic block towers, the crystallization generally occurs adjacent to the magnet face. The effects of nucleation and solution concentration gradients on the crystallization process are also explored. These observations show how the crystallization process is affected by magnetic fields and thus these results have far-reaching effects which most certainly will include crystallization and ion migrations in biology.

The self-assembly and self-organization of water molecules are relevant in many fields of research. When water spontaneously reacts with 2,2,6,6-tetramethylpiperidine (TMP) to form colourless and crystalline discrete needles, only in the exact ratio of 2:1, it is important to understand the phenomenon. Single-crystal X-ray and neutron diffraction data have unveiled that TMP self-assembles around columns of water molecules, and as such, the resulting adduct may be described as a series of molecular water pipes.

Climate driven trends in ocean temperature and primary productivity are projected to differ greatly across the globe, likely triggering variable levels of concern for marine biota and ecosystems. Quantifying these changes, and the complex ways in which resource-dependent communities will need to respond, is inherently difficult. Existing uncertainty about the structure, function and responses of marine ecosystems, means that an ensemble model approach is the most robust means of considering potential ecosystem responses to climate change. In this study, climate-ecological projections of 14 marine ecosystem models for regions around Australian were assessed. The models included Ecopath with Ecosim, Atlantis, intermediate complexity, species distribution, and size spectrum models and were all forced by high-resolution ocean forecasting models. Model results found that each Australian region and fishery will face its own challenges in terms of ecosystem shifts and fisheries management responses over the next 40 years. Across assessment regions, demersal systems appear to be more strongly affected by climate change than pelagic systems, with invertebrate species in shallow waters likely to respond first and to a larger degree. With the assistance of qualitative confidence evaluations, the ensemble approach was useful for identifying the likely state of concern for each functional group and thus management priorities. Simulations that considered trophic interactions and feedbacks result in much more realistic responses to climate change, with implications for future assessments and adaption planning. Study results show that fisheries and their management will need to foster pro-active and flexible adaptation options to make the most of coming opportunities and to minimize risks or negative outcomes.

The Lucite Alpha process is the predominant technology for the preparation of acrylics. This two-stage process involves the palladium-catalysed formation of methyl propanoate from ethene, CO, and methanol, followed by the oxidative formylation of methyl propanoate into methyl methacrylate. A range of bis-1,2-disubstituted aminomethylferrocenes has been prepared and characterised. These complexes serve as precursors to a variety of bulky ferrocenylmethyldiphosphanes that, in turn, function as ligands in the palladium-catalysed process. We describe the crystal structures of five ligand precursors and provide a rationale for their design. In situ catalyst testing on palladium complexes derived from ferrocenylphosphanes demonstrates that these are highly selective (>99.5%) catalysts for the formation of methyl propanoate from ethene, CO, and methanol and have turnover numbers exceeding 50,000. This article credits those researchers who worked on this project in the early days, who received little or no credit for their achievements and endeavours.

ContextConnectivity is an important property of landscapes that shapes populations and ecosystem functioning. We do not know, however, whether and how different types of spatial linkages combine to influence ecological functions, and this hampers their integration into conservation planning.ObjectivesWe used coral reef seascapes in eastern Australia as a model system to test whether the proximity of other reefs (habitat proximity) or the proximity of other habitats (seascape proximity) exert stronger effects on two key ecological functions (herbivory and piscivory).MethodsWe measured rates of herbivory (on fleshy macroalgae) and piscivory (on prey fish) on reefs that differed in their proximity to both other reefs and nearby mangroves and seagrass.ResultsThe extent of habitat proximity between reefs significantly influenced both ecological functions, but in different ways: isolated reefs supported high herbivory but low piscivory, whilst, conversely, reefs that were closer to other reefs supported high piscivory but low herbivory. This was not caused by herbivores avoiding their predators, as the dominant piscivores (small predatory snappers) were too small to consume the dominant herbivores (large rabbitfishes). Seascape proximity (e.g., distance to mangroves or seagrass) was less important in shaping ecological functions on reefs in this system.ConclusionsWe suggest that the effects of seascape configuration on ecological functions depends on the type of spatial linkage, and the ecological functions in question. To better integrate connectivity into conservation, we must develop a deeper understanding of how different spatial linkages combine to shape ecosystem functioning across landscapes.

Connectivity is an important consideration in conservation, but is rarely quantified when assessing marine reserve performance. Mangrove–reef connectivity is known to enhance reserve effectiveness when habitats are close together (<250 m apart). Coral reefs are, however, often farther from mangroves, making it difficult to integrate mangrove–reef connectivity into conservation more widely. To determine if connectivity affects reserve performance beyond 250 m, we examined effects on reef fish in Hervey Bay, Queensland, Australia. Reserves affected fish assemblages and enhanced the abundances of harvested species and key functional groups on reefs within 500 m of mangroves (about 10 times greater inside reserves), but not on isolated reefs. Connectivity can affect reserve performance over broader distances than previously shown. We suggest that connectivity effects on inshore reef fish may simply be amplified on reefs located closest to adjacent mangroves, provided those reefs are within the migratory capabilities of fish. Mangrove–reef connectivity should be viewed as an important conservation target and may be broadly incorporated into reserve design by prioritizing the protection of seascapes where mangroves and reefs are closest.

In this paper, the clean high yielding, synthesis, and structure of the tetraphosphine ligand, 1,1′,2,2′-tetrakis-(di-isopropyl-phosphino)ferrocene, (tdipf), is described. In addition, improved synthesis methods for 1,1′,2,2′-tetrakis(diphenylphosphino)ferrocene, (tppf), and 2,2′-bis-(diphenylphosphino)-1,1′-dibromoferrocene are also reported, and the synthetic method is generalised to include the synthesis of 3,3′-bis-(diphenylphosphino)-1,1′,2,2′-tetrabromoferrocene. The related ligands 2,2′-bis-(iso-propylphosphino)-1,1′-bis-diphenylphosphinoferrocene (diprdppf) and 2,2′-bis-(di-isopropylphosphino)-dibromoferrocene have also been prepared and characterised. The crystal structure of the square planar bimetallic nickel (II) dichloride of tdipf is also described, together with a brief NMR study investigating the synthesis of this and related metal complexes. The crystal structures of the palladium and platinum dichloride complexes of 2,2′-bis-(di-isopropylphosphino)-1,1′-dibromoferrocene, bpdbf, are also discussed in the context of comparison with previously known crystal structures in the same general family. A general discussion on the synthetic methodology is given, along with indications for future research that other researchers might explore.