1,3‐Bis(trimethylsilyl)‐1,3,2‐diazaphospha‐[3]ferrocenophanes 

Abstract

The 2‐tert‐butyl, 2‐phenoxy, and 2‐diethylamino derivatives of 1,3‐bis(trimethylsilyl)‐1,3,2‐diazaphospha‐[3]ferrocenophane were prepared, and the molecular structure of the latter was determined by X‐ray diffraction. The phosphines could be oxidized by their slow reactions with sulfur or selenium, and the molecular structures of three sulfides and one selenide were determined. In contrast, the synthesis of oxides was less straightforward. All new compounds were characterized in solution by multinuclear magnetic resonance methods (1D and 2D 1H, 13C, 15N, 29Si, 31P, and 77Se NMR spectroscopy).

Ferrocene-Containing Polycarbosilazanes via the Alkaline-Earth-Catalyzed Dehydrocoupling of Silanes and Amines

“…When 2 equiv of diphenylsilane was used, 5 persisted as the major product in 70% spectroscopic yield with the remaining products assumed to be linear species, which eluded unambiguous characterization. Although there are several examples of metallocenophanes with nitrogen-containing ansa -bridges (excepting ferrocene-based N-heterocyclic carbenes and numerous examples where the 1,1′-bisamino-, amido-, and imido- ferrocene moiety has been used as a chelating ligand), − compound 5 is of particular interest since it is, to the best of our knowledge, the first example with a N–Si–N bridging unit.…”

A P‐Functionalized [3]Ferrocenophane with a Dynamic SPS‐Bridge

“…We report in this work on the synthesis and characterization of 1,3,2‐dithiaphospha‐[3]ferrocenophanes ( 1 , 2 Scheme 2) that we consider special in two respects. Firstly, the synthesis of type‐ II [3]ferrocenophanes with P−Cl or P−N‐bonds that allow in principle for further post‐derivatization of the ansa ‐bridge has been reported for species with X=O, [6d] NR′, [7d,h] and PR′, [7f] but not for the thia‐derivatives with X=S. Secondly, P‐chloro‐substituted 1 offers an unprecedented opportunity to monitor the bridge‐dynamics in a ferrocenophane‐based phosphine, which was not directly spectroscopically observable in II (X=P t Bu) [7f] and IV [7g] .…”