Facile Phosphorus–Carbon Bond Formation using a Tungsten-Coordinated Phosphirenyl Cation

• Published in: Organometallics Vol. 32; no. 3; pp. 745 - 747
• Main Authors: Jayaraman, Arumugam, Sterenberg, Brian T
• Format: Journal Article
• Language: English
• Published: American Chemical Society 11.02.2013
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om301266x

Reaction of K2[W(CO)5] with Cl2PN-i-Pr2 in the presence of diphenylacetylene leads to the tungsten aminophosphirene complex [W(CO)5{P(N-i-Pr2)C(Ph)C(Ph)}] (1), which can be converted to the chlorophosphirene complex [W(CO)5{P(Cl)C(Ph)C(Ph)}] (2) by reaction with HCl. Chloride abstraction from 2 with excess AlCl3 leads to the tungsten-complexed phosphirenyl cation [W(CO)5{PC(Ph)C(Ph)}][AlCl4] (3). Compound 3 reacts with PPh3 to form a phosphoniophosphirene complex and undergoes electrophilic aromatic substitution with ferrocene to form a ferrocenylphosphirene complex. Chloride abstraction from 2 with silver triflate leads to a phosphirenyl triflate complex, which reacts with PPh3 and ferrocene in the same fashion as 3 but also reacts cleanly with a wider range of substrates, including phenylacetylene and allyltrimethylsilane, to form respectively a phenylalkynylphosphirene complex and an allylphosphirene complex.