Ambiphilie, ein charakteristisches Reaktivitätsprinzip π-gebundener Phosphorheterocyclen

Abstract

Ausgeprägte intramolekulare Reaktionen im Einkristall: 1,3‐Diphosphet kann zum einen als Nucleophil, zum anderen als Elektrophil agieren. Diese Eigenschaft ermöglicht eine temperaturabhängige Ligandverknüpfung bei [(2,4‐Di‐tBu‐1,3‐diphosphet)3Mo], die als topotaktische Reaktion verläuft (siehe Schema). Der neuartige Mechanismus kann zur Klärung eine Reihe von komplexen Ligandverknüpfungsreaktionen beitragen, an denen P‐Heterocyclen beteiligt sind.

Diphospholyl and triphospholyl zirconium π-complexes: Ziegler–Natta oligomerization catalysts and reactive intermediates in P–C cage formation by hydrolysis

“…Compound 7 was first described as the triangular p-complex 7A with an unexplained short distance of 215.1 pm between one phosphorus atom and a ring carbon atom of one of the neighboring ligands [25]. A reinvestigation at low temperature, however, led to the identification of 7B as the ground state of the molecule, where a P-C single bond between two ligands with a length of 198.8 pm is formed at that specific position [26]. Compound 7A serves as the transition state in equilibrium between 7B and its mirror image only (Fig.…”

The Homoleptic Sandwich Anion [Co(P2C2tBu2)2]−: A Versatile Building Block for Phosphaorganometallic Chemistry

“…Interestingly, a free 1,3‐diphosphacyclobuten‐4‐yl radical has been isolated only recently 15. The formation of 3 is reminiscent of the well‐documented ambiphilic behavior of diphosphacyclobutadiene ligands 3a. The methyl group in 3 is bound to one of the phosphorus atoms of a slightly pyramidalized η 4 ‐coordinated P 2 C 2 t Bu 2 ring (sum of angles around P1: 346.41°).…”