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Between Adamantane and Atrane: Intrabridgehead Interactions in the Cage‐Like Phosphane Related to a Novel Tris(homoadamantane) Ring System
Author(s) -
Britvin Sergey N.,
Rumyantsev Andrey M.,
Zobnina Anastasia E.,
Padkina Marina V.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201601637
Subject(s) - adamantane , chemistry , ring (chemistry) , cage , ligand (biochemistry) , crystallography , molecule , atom (system on chip) , stereochemistry , computational chemistry , organic chemistry , receptor , mathematics , combinatorics , biochemistry , computer science , embedded system
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.