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- Title
PhP=CPh<sub>2</sub> and Related Phosphaalkenes: A Solution Equilibrium between a Phosphaalkene and a 1,2-Diphosphetane.
- Authors
Wang, Shuai; Samedov, Kerim; Serin, Spencer C.; Gates, Derek P.
- Abstract
The synthesis of phosphaalkenes, ArP=C(R)Ph ( 1, a: Ar = Ph, R = Ph; b: Ar = o-Tol, R = Ph; c: Ar = Mes, R = H), bearing sterically less hindered substituents is reported. Phosphaalkenes 1a- b were prepared by treating Ph2C=O with ArP(Li)SiMe3, whereas 1c was accessed from the AlCl3-mediated reaction of ArP(SiMe3)2 and PhC(O)H. Both 1a and 1b dimerize to afford their respective 1,2-diphosphetanes ( 2a and 2b). Compound 2a was characterized by X-ray crystallography. Dissolution of pure 2a in THF resulted in a temperature dependent equilibrium with monomer 1a (Δ Ho = -94.6 ± 14.6 kJ mol-1; Δ So = -284 ± 48 J mol-1 K-1). Although monomer E/Z- 1c was identified in solution by its characteristic downfield 31P NMR chemical shift ( δ = 247.1, 231.5), it was accompanied by the formation of what we believe are oligomers ( δ = -25 to 10 ppm, br.). Attempts to trap phosphaalkenes 1a and 1b by treatment with W(CO)5(MeCN) afforded mixtures of complexes W(CO)5( 1a- b) ( 4a- b) and W(CO)4( 1a- b)2 ( 5a- b), the disubstituted species being subjected to X-ray crystallographic characterization ( 5a).
- Subjects
CHEMICAL synthesis; PHOSPHATES; EQUILIBRIUM constant (Chemistry); DIPHOSPHINE; SUBSTITUENTS (Chemistry); X-ray crystallography; OLIGOMERS; DISSOLUTION (Chemistry); MULTIPLE bonds (Chemistry)
- Publication
European Journal of Inorganic Chemistry, 2016, Vol 2016, Issue 26, p4144
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201600599