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On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates.

ABSTRACT: The ambiphilic nature of geometrically constrained Group?15 complexes bearing the N,N-bis(3,5-di-tert-butyl-2-phenolate)amide pincer ligand (ONO3- ) is explored. Despite their differing reactivity towards nucleophilic substrates with polarised element-hydrogen bonds (e.g., NH3 ), both the phosphorus(III), P(ONO) (1?a), and arsenic(III), As(ONO) (1?b), compounds exhibit similar reactivity towards charged nucleophiles and electrophiles. Reactions of 1?a and 1?b with KOtBu or KNPh2 afford anionic complexes in which the nucleophilic anion associates with the pnictogen centre ([(tBuO)Pn(ONO)]- (Pn=P (2?a), As (2?b)) and [(Ph2 N)Pn(ONO)]- (Pn=P (3?a), As (3?b)). Compound 2?a can subsequently be reacted with a proton source or benzylbromide to afford the phosphorus(V) compounds (tBuO)HP(ONO) (4?a) and (tBuO)BzP(ONO) (5?a), respectively, whereas analogous arsenic(V) compounds are inaccessible. Electrophilic substrates, such as HOTf and MeOTf, preferentially associate with the nitrogen atom of the ligand backbone of both 1?a and 1?b, giving rise to cationic species that can be rationalised as either ammonium salts or as amine-stabilised phosphenium or arsenium complexes ([Pn{ON(H)O}]+ (Pn=P (6?a), As (6?b)) and [Pn{ON(Me)O}]+ (Pn=P (7?a), As (7?b)). Reaction of 1?a with an acid bearing a nucleophilic counteranion (such as HCl) gives rise to a phosphorus(V) compound HPCl(ONO) (8?a), whereas the analogous reaction with 1?b results in the addition of HCl across one of the As-O bonds to afford ClAs{(H)ONO} (8?b). Functionalisation at both the pnictogen centre and the ligand backbone is also possible by reaction of 7?a/7?b with KOtBu, which affords the neutral species (tBuO)Pn{ON(Me)O} (Pn=P (9?a), As (9?b)). The ambiphilic reactivity of these geometrically constrained complexes allows some insight into the mechanism of reactivity of 1?a towards small molecules, such as ammonia and water.

SUBMITTER: Robinson TP

PROVIDER: S-EPMC5095867 | biostudies-other | 2016 Oct

REPOSITORIES: biostudies-other

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On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates.

Robinson Thomas P TP Lo Siu-Kwan SK De Rosa Daniel D Aldridge Simon S Goicoechea Jose M JM

Chemistry (Weinheim an der Bergstrasse, Germany) 20160915 44

The ambiphilic nature of geometrically constrained Group 15 complexes bearing the N,N-bis(3,5-di-tert-butyl-2-phenolate)amide pincer ligand (ONO<sup>3-</sup> ) is explored. Despite their differing reactivity towards nucleophilic substrates with polarised element-hydrogen bonds (e.g., NH<sub>3</sub> ), both the phosphorus(III), P(ONO) (1 a), and arsenic(III), As(ONO) (1 b), compounds exhibit similar reactivity towards charged nucleophiles and electrophiles. Reactions of 1 a and 1 b with KOtBu or ...[more]

PMID: 27628576

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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.

Dataset Information

On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates.

Publications

On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates.

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