88000-34-4Relevant academic research and scientific papers
3H-benzophosphepine complexes: Versatile phosphinidene precursors
Borst, Mark L. G.,Bulo, Rosa E.,Gibney, Daniele J.,Alem, Yonathan,De Kanter, Frans J. J.,Ehlers, Andreas W.,Schakel, Marius,Lutz, Martin,Spek, Anthony L.,Lammertsma, Koop
, p. 16985 - 16999 (2007/10/03)
The synthesis of a variety of benzophosphepine complexes [R = Ph, t-Bu, Me; MLn = W(CO)5, Mo(CO)5, Cr(CO)5, Mn(CO)2Cp] by two successive hydrophosphinations of 1,2-diethynylbenzene is discussed in det
The carbene-like behavior of terminal phosphinidene complexes toward olefins. A new access to the phosphirane ring
Marinetti, Angela,Mathey, Fran?ois
, p. 456 - 461 (2008/10/08)
In the presence of copper(I) chloride, (7-R-7-phosphanorbornadiene)P-M(CO)5 complexes (M = Cr, W) decompose around 55°C to give the corresponding terminal phosphinidene complexes RP=M(CO)5. These transient phosphinidene complexes react in situ with olefins to give phosphirane complexes. The stereochemistry of the starting olefin is retained in the phosphirane ring, thus suggesting a concerted process. The reaction with 1,3-dienes yields 2-vinylphosphirane complexes that rearrange around 100°C to the corresponding phospholenes. On the contrary, the reaction with α,β-unsaturated ketones gives directly the 1,2-oxaphospholene complexes, but the formation of an intermediate 2-acylphosphirane cannot be excluded. With methyl methacrylate, the 2-(methoxycarbonyl)phosphirane is formed and is apparently stable. With ethyl vinyl ether, the 2-ethoxyphosphirane transiently obtained is so reactive that neutral water cleaves the P-C(OEt) bond of the ring to give a secondary α-phosphinoacetaldehyde that is stabilized as its P-W(CO)5 complex. An excess of vinyl ether also reacts with the 2-ethoxyphosphirane to give a 2,4-diethoxyphospholane. In all its reactions, PhP=W(CO)5 apparently behaves as a singlet electrophilic carbene.
