A metal/ligand cooperative approach to the reduction of small molecules by metal silylene complexes (R2Si=M) is demonstrated, whereby silicon activates the incoming substrate and mediates net two‐electron transformations by one‐electron redox processes at two metal centers. An appropriately tuned cationic pincer cobalt(I) complex, featuring a central silylene donor, reacts with CO2to afford a bimetallic siloxane, featuring two CoIIcenters, with liberation of CO; reaction of the silylene complex with ethylene yields a similar bimetallic product with an ethylene bridge. Experimental and computational studies suggest a plausible mechanism proceeding by [2+2] cycloaddition to the silylene complex, which is quite sensitive to the steric environment. The CoII/CoIIproducts are reactive to oxidation and reduction. Taken together, these findings demonstrate a strategy for metal/ligand cooperative small‐molecule activation that is well‐suited to 3
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Abstract A metal/ligand cooperative approach to the reduction of small molecules by metal silylene complexes (R2Si=M) is demonstrated, whereby silicon activates the incoming substrate and mediates net two‐electron transformations by one‐electron redox processes at two metal centers. An appropriately tuned cationic pincer cobalt(I) complex, featuring a central silylene donor, reacts with CO2to afford a bimetallic siloxane, featuring two CoIIcenters, with liberation of CO; reaction of the silylene complex with ethylene yields a similar bimetallic product with an ethylene bridge. Experimental and computational studies suggest a plausible mechanism proceeding by [2+2] cycloaddition to the silylene complex, which is quite sensitive to the steric environment. The CoII/CoIIproducts are reactive to oxidation and reduction. Taken together, these findings demonstrate a strategy for metal/ligand cooperative small‐molecule activation that is well‐suited to 3
d metals. -
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Abstract Fungi represent a rapidly cycling pool of carbon (C) and nitrogen (N) in soils. Understanding of how this pool impacts soil nutrient availability and organic matter fluxes is hindered by uncertainty regarding the dynamics and drivers of fungal necromass decomposition.
Here we assessed the generality of common models for predicting mass loss during fungal necromass decomposition and linked the resulting parameters to necromass substrate chemistry. We decomposed 28 different types of fungal necromass in laboratory microcosms over a 90‐day period, measuring mass loss on all types, and N release on a subset of types. We characterised the initial chemistry of each necromass type using: (a) fibre analysis methods commonly used for plant tissues, (b) initial melanin and nitrogen (N) concentrations and (c) Fourier transform infrared (FTIR) spectroscopy to assess the presence of bonds associated with common biomolecules.
We found universal support for an asymptotic model of decomposition, which assumes that fungal necromass consists of an exponentially decomposing ‘fast’ pool, and a ‘slow’ pool that decomposes at a rate approaching zero. The strongest predictor of the fast pool decay rate (
k ) was the proportion of cell soluble components, though initial N concentration also predictedk , albeit more weakly. The size of the slow pool was best predicted by the acid non‐hydrolysable fraction, which was positively correlated with melanin‐associated aromatics. Nitrogen dynamics varied by necromass type, ranging from net N release to net immobilisation. The maximum quantity of N immobilised was inversely related to cell soluble contents andk , as positively related to FTIR spectra associated with cell wall polysaccharides.Collectively, our results indicate that the decomposition of fungal necromass in soils can be described as having two distinct stages that are driven by different components of substrate C chemistry, with implications for rates of N availability and organic matter accumulation in soils.
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