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Complex Chemical Stabilization of Dichlorodiphosphene.

Ulf Vogel¹, Gregor Stößer¹, Manfred Scheer¹

¹Institut für Anorganische Chemie der Universität Karlsruhe 76128 Karlsruhe (Germany) Fax: (+49) 721-661921.

Angewandte Chemie (International Ed. in English)

|May 2, 2018

Summary

The study found that dichlorodiphosphene, unlike its nitrogen analog, adopts a trans configuration. This molecule was successfully stabilized within transition metal complexes for the first time.

Keywords:

P ligands density functional calculations phosphene tungsten

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Area of Science:

Inorganic chemistry
Organometallic chemistry
Computational chemistry

Background:

Nitrogen difluoride (N2F2) exists in a cis configuration.
Phosphorus subhalides (P2X2) were theoretically predicted to adopt a trans configuration.
Stabilization of reactive low-valent phosphorus compounds is challenging.

Purpose of the Study:

To synthesize and characterize the first transition metal complex of dichlorodiphosphene.
To experimentally verify the predicted trans configuration of dichlorodiphosphene.
To explore the coordination chemistry of P2Cl2.

Main Methods:

Density functional theory (DFT) calculations were used to predict the geometry of P2X2.
Synthesis of a transition metal complex containing dichlorodiphosphene (Complex 1).
Characterization of Complex 1 using spectroscopic and crystallographic methods (details not provided in abstract).

Main Results:

DFT calculations predicted a trans configuration for P2X2, contrasting with cis N2F2.
Dichlorodiphosphene (P2Cl2) was successfully stabilized in the coordination sphere of a transition metal.
Formation of the first reported transition metal complex of dichlorodiphosphene, Complex 1.

Conclusions:

The experimental results support the theoretical prediction of a trans configuration for dichlorodiphosphene.
Transition metal coordination provides a viable strategy for stabilizing reactive low-coordinate phosphorus species.
This work opens new avenues for the chemistry of low-valent phosphorus compounds.