21050-13-5Relevant articles and documents
Reactions of undecacarbonyltriferrate with α,β-unsaturated acyl halides. Decomposition of 3-RCH=CHCOOCFe3(CO)10>- to 2-RCH=CHFe2(CO)7 involving transfer of the acyl group from oxygen to iron
Ishihara, Atsushi,Mitsudo, Take-Aki,Watanabe, Yoshihisa
, p. 199 - 208 (1989)
2 (PPN=bis(triphenylphosphine)iminium) (1) reacts with α,β-unsaturated acyl halides in CH2Cl2 at 25 deg C during 15 min to give 3-RCH=CHCOOCFe3(CO)10> (2a, 2b) (2a: R=CH3, 2b: R=Ph), which slowly decomposes to give
Probing the mechanism of the PCl5-initiated living cationic polymerization of the phosphoranimine Cl3P=NSiMe3 using model compound chemistry
Blackstone, Vivienne,Lough, Alan J.,Murray, Martin,Manners, Ian
experimental part, p. 3658 - 3667 (2009/09/24)
New insight into the mechanism of the ambient temperature PCl5-initiatedliving cationic chain growth polycondensation of the N-silylphosphorani mine Cl3P=NSiMe3 (1) to give poly(dichlorophosphazene), [N=PCl2]n,has been provided by studies of model compound chemistry. Investigations of the reactivity of Cl- salts ofthe proposed cationic intermediates [Cl3P=N=PCl3] + ([2] +) and [Cl3PdN-PCl2dNdPCl3] + ([6]+) toward Ph3P=NSiMe3 (3a) provided evidence that under the usual polymerization conditions that involve a high monomer to initiator ratio, propagation occurs at both chain ends. However, analogous studies of near stoichiometric processes suggested that propagation is faster at one chain end, particularly when the chains are short. In addition, experiments involving [Ph3P=N=PPh3][PCl6] ([9][PCl6]) and the N-silylphosphoranimines R3P-NSiMe 3 3a (R = Ph) and 3b (R = p-CF3C6H 4),showed that the [PCl6]- anion, which is formed in the early stages of the polymerization and has hitherto been assumed to be an innocent spectator counteranion, is actually reactive under the r eaction conditions and can initiate oligomerization and polymerization. Finally, the absence of reactions between phosphoranimines 3b or 1 with the Cl- salts of the cations [Ph3P=N-PCl2=N=PPh3]+ ([10a]+), [Ph3P=N-(PCl2=N) 2= PPh3]+ ([5]+), and [Ph3P=N-(PCl 2=N) 3-PPh3]+ ([8]+) with P-Cl bonds located internally but not at the chain ends have shown that chain branching reactions are unlikely to be significant during the polymerization. These results identify key factors that complicate the living PCl5-initiated chain growth polycondensation of 1 and potentially lead to a loss of control over molecular weight and broaden the molecular weight distributions, but also indicate that the polymer formed is essentially linear rather than branched.
Cyclic sulphur-nitrogen compounds and phosphorus reagents: Part XIII-Reactions of cyclic sulphur-nitrogen chlorides with Ph3P-influences of tetiary base, Et3N and the ring size of the cyclothiazyl chloride on the product formation
Mohan, T.,Senthivel, P.,Rao, M. N. Sudheendra
, p. 961 - 966 (2007/10/03)
Similar to the reactions with S4N3Cl and S3N3Cl3, triphenylphosphine reacts with five-membered cyclic sulphur-nitrogen chlorides namely, S3N2Cl and S3N2Cl2 to give triphenylphosphiniminium chloride, Ph3P=NH+2Cl- as the major product.Maximum yield (ca. 90percent) is obtained when triphenylphosphine is reacted with S3N2Cl in acetonitrile at room temperature in 2 : 1 molar ratio.Analogous reactions performed in presence of triethylamine afford two cyclothiazene products containing phosphinimino substituent.The ring size of the S - N chloride seems to determine the nature of phosphiniminocyclothiazenes formed.A rationalization of the results obtained has been attempted.
