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Geometrically constrained square pyramidal phosphoranide† † Electronic supplementary information (ESI) available: NMR, EPR, MS, experimental and computational details (PDF). CCDC 2122218–2122224. For ESI and crystallographic data in CIF or other electronic format see https://doi.org/10.1039/d2sc01060g

ABSTRACT: Geometrical constriction of main group elements leading to a change in the reactivity of these main group centers has recently become an important tool in main group chemistry. A lot of focus on using this modern method is dedicated to group 15 elements and especially to phosphorus. In this work, we present the synthesis, isolation and preliminary reactivity study of the geometrically constrained, square pyramidal (SP) phosphoranide anion (1−). Unlike, trigonal bipyramidal (TBP) phosphoranides that were shown to react as nucleophiles while their redox chemistry was not reported, 1− reacts both as a nucleophile and reductant. The chemical oxidation of 1− leads to a P–P dimer (1-1) that is formed via the dimerization of unstable SP phosphoranyl radical (1˙), an unprecedented decay pathway for phosphoranyl radicals. Reaction of 1− with benzophenone leads via a single electron transfer (SET) to 1-OK and corresponding tetraphenyl epoxide (4). Geometrically constrained, square pyramidal phosphoranide was synthesized, and its reactivity study showed that it is both a nucleophile and reductant.

SUBMITTER: Volodarsky S

PROVIDER: S-EPMC9132080 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature

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Project description:BackgroundWe suggest a new type of modeling approach for the coarse grained, particle-based spatial simulation of combinatorially complex chemical reaction systems. In our approach molecules possess a location in the reactor as well as an orientation and geometry, while the reactions are carried out according to a list of implicitly specified reaction rules. Because the reaction rules can contain patterns for molecules, a combinatorially complex or even infinitely sized reaction network can be defined. For our implementation (based on LAMMPS), we have chosen an already existing formalism (BioNetGen) for the implicit specification of the reaction network. This compatibility allows to import existing models easily, i.e., only additional geometry data files have to be provided.ResultsOur simulations show that the obtained dynamics can be fundamentally different from those simulations that use classical reaction-diffusion approaches like Partial Differential Equations or Gillespie-type spatial stochastic simulation. We show, for example, that the combination of combinatorial complexity and geometric effects leads to the emergence of complex self-assemblies and transportation phenomena happening faster than diffusion (using a model of molecular walkers on microtubules). When the mentioned classical simulation approaches are applied, these aspects of modeled systems cannot be observed without very special treatment. Further more, we show that the geometric information can even change the organizational structure of the reaction system. That is, a set of chemical species that can in principle form a stationary state in a Differential Equation formalism, is potentially unstable when geometry is considered, and vice versa.ConclusionsWe conclude that our approach provides a new general framework filling a gap in between approaches with no or rigid spatial representation like Partial Differential Equations and specialized coarse-grained spatial simulation systems like those for DNA or virus capsid self-assembly.

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