Between Adamantane and Atrane: Intrabridgehead Interactions in the Cage-Like Phosphane Related to a Novel Tris(homoadamantane) Ring System
| Autor: | M. V. Padkina, Anastasia E. Zobnina, Andrey M. Rumyantsev, Sergey N. Britvin |
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| Rok vydání: | 2016 |
| Předmět: |
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Molecular Magnetic Resonance Spectroscopy Stereochemistry Phosphines Adamantane Electrons Electronic structure 010402 general chemistry Ring (chemistry) Ligands 01 natural sciences Methylation Catalysis Coordination complex chemistry.chemical_compound Organophosphorus Compounds Polycyclic Compounds chemistry.chemical_classification Aqueous solution 010405 organic chemistry Ligand Organic Chemistry Tridecane Water General Chemistry 0104 chemical sciences chemistry Atrane Solubility |
| Zdroj: | Chemistry (Weinheim an der Bergstrasse, Germany). 22(40) |
| ISSN: | 1521-3765 |
| Popis: | Herein, we report unusual four-center interactions in the novel cage-like phosphane, 1,4,7-triaza-9-phosphatricyclo[5.3.2.1(4,9) ]tridecane (CAP). This water-soluble ligand, the first example of a tris(homoadamantane) ring system, can be considered a macrocyclic homologue of the well-known PTA (1,3,5-triaza-7-phosphaadamantane). However, (31) P NMR spectroscopic anomalies of CAP follow those typical for the bi-/tricyclic atrane systems. Another atrane-like feature of CAP is the ability of one nitrogen atom to undergo out-in pyramidal inversion. The latter is associated with a substantial decrease in the intracage N-N and P-N distances. Analysis of electron density distribution [molecular electrostatic potential (MESP) and atoms-in-molecules (AIM) approaches] suggests that the P and N atoms in the pyramidally inverted CAP derivatives are involved in interactions resulting in accumulation of electron density at the center of the phosphane cage. The latter can reliably explain the stereoelectronic and NMR anomalies of the new ligand. The semi-flexible CAP cage populates the structural niche between the rigid adamantine skeleton of PTA and flexible atrane systems and can be regarded as an alternative to PTA in aqueous coordination chemistry. |
| Databáze: | OpenAIRE |
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