Controllable access to P-functional [3]ferrocenophane and [4]ferrocenophane frameworks

Abstract

Condensation of 1,1′-diaminoferrocenes with PCl3 gives access to P-halo-diazaphospha-[3]ferrocenophanes and [4]ferrocenophane-annelated tetraphosphetanes, which can undergo multiple oxidation in both ferrocene and aminophosphine units.

Bis‐[3]Ferrocenophanes with Central >E−E’< Bonds (E, E’=P, SiH): Preparation, Properties, and Thermal Activation

“…Hybrid structure 9 displays similar electrochemical behavior, although more redox events are detectable. The first oxidation occurs at a potential of −0.26(1) V (vs. Fc/Fc + ), which is in the expected range for amino‐substituted ferrocenophanes, as an irreversible process (Figure S7). At higher potential, two quasi reversible oxidation processes (0.02(1) and 0.13 (1) V vs. Fc/Fc + ) were detected using differential pulse techniques.…”

“…Nitrogen‐containing bis‐ferrocenophanes are accessible starting from 1,1′‐diaminoferrocenes. Base‐promoted condensation of 13 a with PCl 3 followed by reductive coupling of the spectroscopically detectable 2‐chloro‐1,3,2‐diazaphospha‐[3]ferrocenophane 14 a with magnesium yields tetraaza‐bis[3]ferrocenophane 8 . Finally, diaza‐bis‐[3]ferrocenophane 9 , which can be regarded as a link between 4 and 8 , is obtained via salt metathesis between 14 b and 3 (Scheme ).…”

A Ferrocenophane-Based Diaminophosphenium Ion

“…Scheme 1. Formation of [3] The ansa bridge is characterized by short P−N distances (P−N 1.619(3), 1.628(3) Å vs values of 1.664(2)−1.730(1) Å in previously reported neutral NPN-[3]ferrocenophanes 9,17 ) and planar coordination at the nitrogen atoms (sums of bond angles 358.9(9) and 359.3(9)°). The staggering of the Cp rings (dihedral angle δ = 9.1(1)°) results in a skewed, C 2symmetric conformation of the ferrocenophane unit in which the nitrogen coordination planes deviate (torsional angle 17°) from the parallel alignment, granting optimum NPN π conjugation.…”

“…[3]Ferrocenophanes 1a,b were prepared as described. 9 Cyclic voltammetry studies on 0.1 mM solutions of the samples in CH 2 Cl 2 (dried over CaH 2 , distilled, and stored over 3 Å molecular sieves under an argon atmosphere) containing [nBu 4 N][PF 6 ] (concentration 0.1 M) as the conducting salt were carried out under an inert argon atmosphere (in the case of 2c in a MBraun acrylic glovebox GB2202-C-VAC). The setup consisted of a three-electrode cell with a platinum disk as the working electrode, a silver spiral as the counter electrode, and a silver pseudo reference electrode.…”

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] .…”