Saint-Denis, Tyler G. and Wheeler, T. Alexander and Chen, Qingchuan and Balazs, Gabor and Settineri, Nicholas S. and Scheer, Manfred and Tilley, T. Don (2024) A Ruthenophosphanorcaradiene as a Synthon for an Ambiphilic Metallophosphinidene. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 146 (7). pp. 4369-4374. ISSN 0002-7863, 1520-5126
Full text not available from this repository. (Request a copy)Abstract
Reaction of the ruthenium carbene complex Cp*(IPr)RuCl (1) (IPr = 1,3-bis(Dipp)imidazol-2-ylidene; Dipp = 2,6-diisopropylphenyl) with sodium phosphaethynolate (NaOCP) led to intramolecular dearomatization of one of the Dipp substituents on the Ru-bound carbene to afford a Ru-bound phosphanorcaradiene, 2. Computations by DFT reveal a transition state characterized by a concerted process whereby CO migrates to the Ru center as the P atom adds to the pi system of the aryl group. The phosphanorcaradiene possesses ambiphilic properties and reacts with both nucleophilic and electrophilic substrates, resulting in rearomatization of the ligand aryl group with net P atom transfer to give several unusual metal-bound, P-containing main-group moieties. These new complexes include a metallo-1-phospha-3-azaallene (Ru & horbar;P & boxH;C & boxH;NR), a metalloiminophosphanide (Ru & horbar;P & boxH;N & horbar;R), and a metallophosphaformazan (Ru & horbar;P(& boxH;N & horbar;N & boxH;CPh2)(2)). Reaction of 2 with the carbene 2,3,4,5-tetramethylimidazol-2-ylidene (IMe4) produced the corresponding phosphaalkene DippP & boxH;IMe4.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | PHOSPHORUS TRIPLE BOND; RAY CRYSTAL-STRUCTURE; PHOSPHINIDENE COMPLEXES; RUTHENIUM COMPLEXES; TUNGSTEN COMPLEXES; MOLYBDENUM; REACTIVITY; SILYLENE; ACCESS; GENERATION; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 09 Dec 2025 07:25 |
| Last Modified: | 09 Dec 2025 07:25 |
| URI: | https://pred.uni-regensburg.de/id/eprint/64068 |
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