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A kinetically stabilized ferrocenyl diphosphene: synthesis, structure, properties, and redox behavior
Noriyoshi Nagahora1, Takahiro Sasamori, Nobuhiro Takeda
1Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|October 30, 2004
Summary
A stable ferrocenyl diphosphene, a compound featuring a phosphorus-phosphorus double bond, was synthesized and characterized. This new diphosphene exhibits remarkable stability in solid and solution states, confirmed by spectroscopic and crystallographic analyses.
Area of Science:
- Organometallic Chemistry
- Main Group Chemistry
- Phosphorus Chemistry
Background:
- Diphosphenes, compounds with a phosphorus-phosphorus double bond, are reactive species.
- Stabilization of diphosphenes is crucial for their study and application.
- Ferrocene-containing compounds offer unique electronic and structural properties.
Purpose of the Study:
- To synthesize and characterize a novel, stable ferrocenyl diphosphene.
- To investigate the structural, spectroscopic, and electrochemical properties of the new compound.
- To explore the electronic structure and bonding in the ferrocenyl diphosphene.
Main Methods:
- Dehydrochlorination reaction using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
- Nuclear Magnetic Resonance (NMR) spectroscopy (31P NMR).
- X-ray crystallographic analysis.
- Cyclic voltammetry.
- Density Functional Theory (DFT) calculations.
Main Results:
- Successful synthesis of a stable ferrocenyl diphosphene [Tbt-P==P-Fc] (1) in good yield.
- Characterization by 31P NMR and X-ray crystallography confirmed an unsymmetrically substituted trans-diphosphene structure.
- Short phosphorus-phosphorus bond length (2.0285(15) Å) indicates significant P=P double bond character.
- Electrochemical studies revealed reversible redox couples, supported by DFT calculations of frontier orbitals.
Conclusions:
- A highly stable ferrocenyl diphosphene was synthesized, overcoming typical reactivity challenges.
- The compound exhibits a trans-diphosphene structure with a notable P=P double bond.
- Its electronic structure involves contributions from both the diphosphene moiety and the ferrocene unit.