Activation of phosphines with borane

2‐Aryl‐dibenzo‐1,2‐oxaphosphorine as a ligand in borane and in Pt(II) complexes

“…By-products 4, 5, and 6-1 were identified by 31 P NMR and MS. The P-ligands are usually protected against oxidation as borane complexes [6]. The arylphosphinites (2a and 2b) were reacted with dimethylsulfide borane to give the phosphiniteboranes (7a and 7b, respectively) that were characterized after purification by 31 P, 11 B, and 13 C NMR spectral parameters (Scheme 2).…”

Redox‐Active 17‐ and 19‐Membered Metallamacrocycles Incorporating Tetrathiafulvalene

“…The use of phosphane-borane substituents in the synthesis of the target TTFs presents several advantages as they are very stable compared to phosphane derivatives towards the Scheme 1. usual oxidizing or electrophilic reagents, and very easy to handle and to purify. [6,7] The bis(cyanoethylthioTTF) 3 was treated with cesium hydroxide and reacted with the bromobutyldiphenylphosphane-borane leading to TTF 5. Decomplexation of the phosphane-borane complex was performed in the presence of DABCO under an inert atmosphere to give the bis[(diphenylphosphanyl)butylthio]TTF 2.…”

Scope and Limitations of the Peterson Olefination Reaction as a Route to Vinylidene Phosphanes

“…It has been reported previously that α-lithiated phosphane-borane complexes behave similarly to α-lithiated phosphane oxides and undergo Horner-type elimination on treatment with aldehydes to give the corresponding alkenes. [14] The reaction between [{nPr 2 P(BH 3 )}(Me 3 Si) 2 C]Li and paraformaldehyde may, therefore, proceed by either a Peterson or a HornerϪWittig-type olefination pathway to give a phosphane-substituted or a silyl-substituted alkene, respectively (Scheme 6). However, we see no evidence for the HornerϪWittig product in this reaction, consistent with previous observations on substrates where competitive Horner and Peterson olefinations may take place.…”

“…Isolated yield 5.12 g, 80%. C 14 17 mmol) in diethyl ether (100 mL) was added, dropwise, a solution of nPrMgCl in diethyl ether (52.17 mL, 0.104 mol). The solution was allowed to attain room temperature and was stirred for 12 h. Deoxygenated water (50 mL) was added and the organic layer was dried with activated 4-Å molecular sieves.…”