88000-32-2Relevant academic research and scientific papers
The Reaction of Terminal Phosphinidene Complexes [RP-W(CO)5] with Vinylboronic Acids: Cycloaddition vs. P-C Bond Formation
Ng, Yong Xiang,Mathey, Franois
supporting information, p. 616 - 619 (2016/02/27)
The reaction of terminal phosphinidene complexes [RP-W(CO)5] with vinylboronic acids is very sensitive to the presence or absence of solid K3PO4 in suspension in the reaction medium. The products are phosphirane complexes without the salt and secondary vinylphosphine complexes in the presence of the salt. This shift of the reaction pathway is explained by the formation of vinyborates in the presence of potassium phosphate.
The reactivity of a terminal phosphinidene complex toward styrenes
Lammertsma, Koop,Chand, Pooran,Yang, Suh-Wan,Hung, Jul-Te
, p. 1875 - 1876 (2008/10/08)
The Hammett reaction constant for the reaction of the terminal phosphinidene complex [Ph-P=W-(CO)5], as generated from the appropriate 7-phosphanorbornadiene complex, toward styrenes is reported and compared to those of free carbenes. The mild electrophilicity supports the unencumbered carbene-like nature of the phosphinidene complex and suggests a concerted addition to olefins with a slightly polar transition state.
Ring opening of three-membered heterocycles by terminal phosphinidene complexes
Marinetti, Angela,Mathey, Fran?ois
, p. 2189 - 2191 (2008/10/08)
(Phenylphosphinidene)pentacarbonyltungsten as produced by thermal decomposition of the appropriate 7-phosphanorbornadiene complex reacts with phenyloxirane to give (2,4-diphenyl-1,3,2-dioxaphospholane)-and (1,2-diphenylphosphirane)pentacarbonyltungsten complexes. Their formation is explained by the insertion of the phosphinidene into the oxirane ring giving a transient 1,2-oxaphosphetane, which then undergoes a [2 + 2] cycloreversion. With 1-tert-butyl-2-phenylaziridine, the same insertion takes place but the isomeric 1,2-azaphosphetane complexes thus formed are thermally stable. With trans-2,3-diphenylthiirane, decomposition into stilbene and formation of phosphirane complexes take place in lieu of the expected insertion.
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.
