Structures of tetrasilylmethane derivatives C(SiXMe2)4 (X = H, F, Cl, Br) in the gas phase and their dynamic structures in solution.

The structures of the molecules C(SiXMe2)4 (X = H, F, Cl, Br) have been determined by gas electron diffraction (GED). Ab initio calculations revealed nine potential minima for each species, with significant ranges of energies. For the H, F, Cl, and Br derivatives nine, seven, two, and two conformers were modelled, respectively, as they were quantum-chemically predicted to be present in measurable quantities. Variable-temperature 1H and 29Si solution-phase NMR studies and, where applicable, 13C NMR, 1H/29Si NMR shift-correlation, and 1H NMR saturation-transfer experiments are reported for C(SiXMe2)4 (X = H, Cl, Br, and also I). At low temperature in solution two conformers (one C1-symmetric and one C2-symmetric) are observed for each of C(SiXMe2)4 (X = Cl, Br, I), in agreement with the isolated molecule ab initiocalculations carried out as part of this work for X = Cl, Br. C(SiHMe2)4 is present as a single C1-symmetric conformer in solution at the temperatures at which the NMR experiments were performed

Structures of tetrasilylmethane derivatives (XMe2Si)2C(SiMe3)2 (X = H, Cl, Br) in the gas phase, and their dynamic structures in solution

The structures of the molecules (XMe2Si)2C(SiMe3)2, where X = H, Cl, Br, have been determined by gas electron diffraction (GED) using the SARACEN method of restraints, with all analogues existing in the gas phase as mixtures of C1- and C2-symmetric conformers. Variable temperature 1H and 29Si solution-phase NMR studies, as well as 13C NMR and 1H/29Si NMR shift correlation and 1H NMR saturation transfer experiments for the chlorine and bromine analogues, are reported. At low temperatures in solution there appear to be two C1 conformers and two C2 conformers, agreeing with the isolated-molecule calculations used to guide the electron diffraction refinements. For (HMe2Si)2C(SiMe3)2 the calculations indicated six conformers close in energy, and these were modeled in the GED refinement

Biogeomorphology, quo vadis? : On processes, time, and space in biogeomorphology

Biogeomorphology has been expanding as a discipline, due to increased recognition of the role that biology can play in geomorphic processes, as well as due to our increasing capacity to measure and quantify feedbacks between biological and geomorphological systems. Here, we provide an overview of the growth and status of biogeomorphology. This overview also provides the context for introducing this special issue on biogeomorphology, and specifically examines the thematic domains of biogeomorphological research, methods used, open questions and conundrums, problems encountered, future research directions, and practical applications in management and policy (e.g. Nature based solutions). We find that whilst biogeomorphological studies have a long history, there remain many new and surprising biogeomorphic processes and feedbacks that are only now being identified and quantified. Based on the current state of knowledge, we suggest that linking ecological and geomorphic processes across different spatio‐temporal scales emerges as the main research challenge in biogeomorphology, as well as the translation of biogeomorphic knowledge into management approaches to environmental systems. We recommend that future biogeomorphic studies should help to contextualise environmental feedbacks by including the spatio‐temporal scales relevant to the organism(s) under investigation, using knowledge of their ecology and size (or metabolic rate). Furthermore, in order to sufficiently understand the ‘engineering’ capacity of organisms, we recommend studying at least the time period bounded by two disturbance events, and recommend to also investigate the geomorphic work done during disturbance events, in order to put estimates of engineering capacity of biota into a wider perspective. Finally, the future seems bright, as increasingly inter‐disciplinary and longer‐term monitoring are coming to fruition, and we can expect important advances in process understanding across scales and better informed modelling effort

The gas-phase structure and some reactions of the bulky primary silane (Me₃Si)₃CSiH₃ and the solid-state structure of the bulky dialkyl disilane [(Me₃Si)₃CSiH₂]₂

The molecular structure of the bulky primary silane, (Me3Si)3CSiH3, in the gas phase has been determined by electron diffraction. Photolysis of (Me3Si)3CSiH3 affords a convenient route to the bulky dialkyl disilane, [(Me3Si)3CSiH2]2, which is the first 1,2-dialkyldisilane to be structurally characterised by single-crystal X-ray diffraction. The disilane has an unusually large Si–Si–C angle of 120.05(9)°.</p