Diphospha[2]ferrocenophane (alias 1,4‐Dihydrotetraphosphaneoxide): Stereoselective Formation via Hydrolytic PP Bond Formation

Abstract

Connected by water: Water, which usually cleaves the PP bond in diphosphenes, can also be used for PP bond formation. This has been demonstrated for a metallocene‐bridged bisdiphosphene with both PP units in the proximity. The resulting ferrocenophane contains an H‐terminated linear P4 chain (see scheme) for which only a limited number of stereoisomers is observed owing to structural restraints.

Metallated [3]Ferrocenophanes Containing P3M Bridges (M = Li, Na, K) §

“…All other reagents were purchased and used without further purification. 1 H, 13 C, and 31 P NMR spectra were recorded on a Varian VNMRS-500 MHz spectrometer (Varian Inc., Palo Alto, CA, USA) at room temperature using tetramethylsilane (TMS) as the external reference for 1 H and 13 C nuclei. 13 C-1 H correlation was used for the detailed chemical shift assignments in 2.…”

“…1 H, 13 C, and 31 P NMR spectra were recorded on a Varian VNMRS-500 MHz spectrometer (Varian Inc., Palo Alto, CA, USA) at room temperature using tetramethylsilane (TMS) as the external reference for 1 H and 13 C nuclei. 13 C-1 H correlation was used for the detailed chemical shift assignments in 2. For multiplets, chemical shifts were reported as The heteronuclear NMR data did not follow a clear trend along the series of alkali-metal cations from Li + to K + in line with observations reported in the literature [24].…”

“…In a similar vein, unsaturated phosphorus-rich phosphanides were employed as building blocks for remarkable supramolecular architectures at the limits of molecular chemistry [7][8][9]. Based on our own efforts in the chemistry of phosphorus-rich ferrocenophanes, we became interested in exploring the metallation of a P-H functionalized bridging unit in a fully phosphorus-bridged [3]ferrocenophane [10][11][12][13]. Herein, we report the results of our investigation targeting the metallation of a stereochemically predefined secondary triphosphane constrained by the [3]ferrocenophane scaffold.…”

A fluoroaryl substituent with spectator function: Reactivity and structures of cyclic and acyclic HF4C6-substituted phosphanes

“…Consequently, electronic deactivation of the P@P group is likely to be the crucial factor. Recently, we and others observed the formation of P-rich compounds from diphosphenes [15][16][17]. Phosphorus rich compounds are of growing interest as stable activated products of white phosphorus [18,19].…”

[3]Ferrocenophanes with the bisphosphanotetryl bridge: inorganic rings on the way to tetrylenes

“…5,6 For bridging units with n = 2, 3 some ring tilts may still be present but the tendency for thermal ROP is significantly reduced. [7][8][9] Recently the unique setting in [3]ferrocenophanes has been used to prepare ferrocenylene bridged carbenes where for the corresponding cation direct interactions between iron and the cationic carbon atom have been suggested. 10,11 Owing to our own interest in the low-coordinate chemistry of group 14 elements we wondered whether it might be feasible to embed heavier tetrylenes into a bridging unit of a [3]ferrocenophane with flanking phosphanyl groups.…”