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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. 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 -system of the aryl group. The phosphanorcaradiene possesses ambiphilic properties and reacts with both nucleophilic and electrophilic substrates, resulting in re-aromatization 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-P=C=NR), a metallo-iminophosphanide (Ru-P=N-R), and a metallo-phosphaformazan (Ru-P(=N-N=CPh2)2). Reaction of 1 with the carbene 2,3,4,5-tetramethylimidazol-2-ylidene (IMe4) produced the corresponding phosphaalkene DippP=IMe4.
Supplementary materials
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Supporting Information
Description
The Supporting information contains synthetic details, crystallographic data, full characterization data (e.g. NMR, IR, EA data, etc.), as well as computational details.
Accession Codes 2312066 (2), 2312067 (3), 2312062 (4), 2312063 (5), 2312064 (6) and 2312065 (7) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.ac.uk/data_request/cif or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre,12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
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