Computational Insight into the Rh-Mediated Activation of White Phosphorus

Schoeller W (2011)
Inorganic Chemistry 50(1): 22-29.

Journal Article | Published | English

No fulltext has been uploaded

Abstract
Density functional calculations on the reaction of white phosphorus with the ligand bis(diphenylphosphino)methyl (dppm) at a rhodium center are presented. The cationic transition metal fragment can react as a nucleophilic as well as an electrophilic species, driven by a simple twisting of the four-membered rings. As a consequence of the conformational controlled philicity, the insertion reaction into white phosphorus occurs with a small energy barrier. The white phosphorus tetrahedron can be chelated by two cationic transition metal fragments into an opened bicyclobutane moiety, strongly stabilized by pi-stacking interactions of the phenyl groups at the two transition metal fragments. It causes a 2:1 coordination; in the first stage of the reaction two molecules of the fragment add to one molecule of white phosphorus. The resulting dicationic complex easily undergoes dissociation into a cationic monoaddition product plus one cationic transition metal fragment. The ring expansion reaction of one ligand is explained by a j-step mechanism in one intermediary product. One ligand of the transition metal fragment dissociates and facilitates, by a cascade of low-energy processes, the rearrangement of the P-4-moiety. Under bipyramid formation a PP-bond is broken, and the free ligand finally attaches to one phosphorus atom. Overall the reaction can be divided in low-energy processes, which pass through different unstable intermediates and more high-energy processes, requiring ligand dissociation.
Publishing Year
ISSN
eISSN
PUB-ID

Cite this

Schoeller W. Computational Insight into the Rh-Mediated Activation of White Phosphorus. Inorganic Chemistry. 2011;50(1):22-29.
Schoeller, W. (2011). Computational Insight into the Rh-Mediated Activation of White Phosphorus. Inorganic Chemistry, 50(1), 22-29.
Schoeller, W. (2011). Computational Insight into the Rh-Mediated Activation of White Phosphorus. Inorganic Chemistry 50, 22-29.
Schoeller, W., 2011. Computational Insight into the Rh-Mediated Activation of White Phosphorus. Inorganic Chemistry, 50(1), p 22-29.
W. Schoeller, “Computational Insight into the Rh-Mediated Activation of White Phosphorus”, Inorganic Chemistry, vol. 50, 2011, pp. 22-29.
Schoeller, W.: Computational Insight into the Rh-Mediated Activation of White Phosphorus. Inorganic Chemistry. 50, 22-29 (2011).
Schoeller, Wolfgang. “Computational Insight into the Rh-Mediated Activation of White Phosphorus”. Inorganic Chemistry 50.1 (2011): 22-29.
This data publication is cited in the following publications:
This publication cites the following data publications:

Export

0 Marked Publications

Open Data PUB

Web of Science

View record in Web of Science®

Sources

PMID: 21121694
PubMed | Europe PMC

Search this title in

Google Scholar