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Geometrically Constrained Cationic Low-Coordinate Tetrylenes: Highly Lewis Acidic σ-Donor Ligands in Catalytic Systems.

ABSTRACT: A novel non-innocent ligand class, namely cationic single-centre ambiphiles, is reported in the phosphine-functionalised cationic tetrylene Ni⁰ complexes, [^PhR DippENi(PPh₃ )₃ ]⁺ (4 a/b (Ge) and 5 (Sn); ^PhR Dipp={[Ph₂ PCH₂ SiR₂ ](Dipp)N}^- ; R=Ph, ⁱ Pr; Dipp=2,6-ⁱ Pr₂ C₆ H₃ ). The inherent electronic nature of low-coordinate tetryliumylidenes, combined with the geometrically constrained [N-E-Ni] bending angle enforced by the chelating phosphine arm in these complexes, leads to strongly electrophilic E^II centres which readily bind nucleophiles, reversibly in the case of NH₃ . Further, the Ge^II centre in 4 a/b readily abstracts the fluoride ion from [SbF₆ ]^- to form the fluoro-germylene complex ^PhR DippGe(F)Ni(PPh₃ )₃ 9, despite this Ge^II centre simultaneously being a σ-donating ligand towards Ni⁰ . Alongside the observed catalytic ability of 4 and 5 in the hydrosilylation of alkynes and alkenes, this forms an exciting introduction to a multi-talented ligand class in cationic single-centre ambiphiles.

SUBMITTER: Keil PM

PROVIDER: S-EPMC9302135 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature

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Geometrically Constrained Cationic Low-Coordinate Tetrylenes: Highly Lewis Acidic σ-Donor Ligands in Catalytic Systems.

Keil Philip M PM Hadlington Terrance J TJ

Angewandte Chemie (International ed. in English) 20220111 8

A novel non-innocent ligand class, namely cationic single-centre ambiphiles, is reported in the phosphine-functionalised cationic tetrylene Ni0 complexes, [PhR DippENi(PPh3 )3 ]+ (4 a/b (Ge) and 5 (Sn); PhR Dipp={[Ph2 PCH2 SiR2 ](Dipp)N}- ; R=Ph, i Pr; Dipp=2,6-i Pr2 C6 H3 ). The inherent electronic nature of low-coordinate tetrylium ...[more]

PMID: 34818461

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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

Geometrically Constrained Cationic Low-Coordinate Tetrylenes: Highly Lewis Acidic σ-Donor Ligands in Catalytic Systems.

Publications

Geometrically Constrained Cationic Low-Coordinate Tetrylenes: Highly Lewis Acidic σ-Donor Ligands in Catalytic Systems.

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