An Isolable Phosphaethynolatoborane and Its Reactivity. Issue 8 (25th January 2018)

• Record Type: Journal Article
• Authors: Wilson, Daniel W. N.; Hinz, Alexander; Goicoechea, Jose M.
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 8(2018)
• Page Start: 2188
• Page End: 2193
• Publication Date: 2018-01-25
• Subjects: 1, 3, 2-diazaboroles -- 1H-diphosphirenes -- 2-phosphaethynolates -- phosphalkenes -- phosphorus; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201712624
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The synthesis and characterization of a stable phosphaethynolatoborane, [B]OCP (1, [B]=N, N′‐bis(2, 6‐diisopropylphenyl)‐2, 3‐dihydro‐1H‐1, 3, 2‐diazaboryl), is described. The increased triple bond character of the P−C bond in1 relative to the free ion (PCO − ) is probed in a series of reactivity studies. Compound1 readily dimerises in donor solvents to afford a cyclic five‐membered 6π‐aromatic compound, cyclo‐P2 {C[B]}O{CO[B]} (2 ), which decarbonylates on UV irradiation. By contrast the nickel‐mediated dimerisation of1 affords the isomeric diphosphacyclobutene [P(CO[B])]2 . When1 is reacted with organolithium reagents such as MesLi (Mes=2, 4, 6‐trimethylphenyl), the boryl moiety shifts and the formation of the lithoxy‐boryl‐phosphaalkene [LiOC[B]P(Mes)]2 was observed. The reactivity of this species towards electrophiles is also described. Abstract : BOCParty : The synthesis, characterization, and reactivity of a stable phosphaethynolatoborane, [B]OCP (1, [B]= N, N ′‐bis(2, 6‐diisopropylphenyl)‐2, 3‐dihydro‐1 H ‐1, 3, 2‐diazaboryl), is described.