A New Route to Macrobicyclic Dibridgehead Diphopsphines P((CH ₂ ) n ) ₃ P; Reductive Demetalation of Cage-Like Fe(CO) ₃ Adducts
- 1Chemistry, Texas A&M University, Department of Chemistry, Texas A&M University, College Station, Texas, United States, 77842-3012
Abstract
When THF solutions of cage-like trans-Fe(CO) 3 (P((CH 2 ) n ) 3 P) ( 1 , n = a /10, b /12, c /14, d /16, e /18) are exposed to a potassium mirror, reduction occurs to give ferrate salts of the formula 2K + [(R 3 P)(CO) 3 Fe] 2– , as supported by IR data. Following additions of excess CO and methanol, the dibridgehead diphosphines P((CH 2 ) n ) 3 P ( 1a-e ) are isolated as white solids in 61-98% yields (average 80%) as mixtures of in/in and out/out isomers that interconvert by homeomorphic isomerization. This protocol represents an alternative to a photochemical demetalation that requires PMe 3 , as well as oxidative recipes that give dibridgehead diphosphine dioxides 1a-e ·2O with byproducts that are difficult to remove. The practicality of the new route is demonstrated by a half gram-scale synthesis of 1b .
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BibTeX
@misc{popovic2026route,
title = {{A New Route to Macrobicyclic Dibridgehead Diphopsphines P((CH ₂ ) n ) ₃ P; Reductive Demetalation of Cage-Like Fe(CO) ₃ Adducts}},
author = {Simon M. Popovic and John A. Gladysz},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010058/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010058/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - A New Route to Macrobicyclic Dibridgehead Diphopsphines P((CH ₂ ) n ) ₃ P; Reductive Demetalation of Cage-Like Fe(CO) ₃ Adducts
AU - Simon M. Popovic
AU - John A. Gladysz
PY - 2026
DA - 2026/10/07
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010058/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010058/v1
AB - When THF solutions of cage-like trans-Fe(CO) 3 (P((CH 2 ) n ) 3 P) ( 1 , n = a /10, b /12, c /14, d /16, e /18) are exposed to a potassium mirror, reduction occurs to give ferrate salts of the formula 2K + [(R 3 P)(CO) 3 Fe] 2– , as supported by IR data. Following additions of excess CO and methanol, the dibridgehead diphosphines P((CH 2 ) n ) 3 P ( 1a-e ) are isolated as white solids in 61-98% yields (average 80%) as mixtures of in/in and out/out isomers that interconvert by homeomorphic isomerization. This protocol represents an alternative to a photochemical demetalation that requires PMe 3 , as well as oxidative recipes that give dibridgehead diphosphine dioxides 1a-e ·2O with byproducts that are difficult to remove. The practicality of the new route is demonstrated by a half gram-scale synthesis of 1b .
ER -