2117-20-6Relevant academic research and scientific papers
Reactions of phosphine oxides with bromophosphoranimines; Synthesis and unusual rearrangements of O-donor stabilized phosphoranimine cations
Bendle, Martin,Huynh, Keith,Haddow, Mairi F.,Manners, Ian
scheme or table, p. 10292 - 10302 (2011/12/02)
Reaction of phosphine oxides R3P=O [R = Me (1a), Et (1c), iPr (1d) and Ph (1e)], with the bromophosphoranimines BrPR′R″P=NSiMe3 [R′ = R″ = Me (2a); R′ = Me, R″ = Ph (2b); R′ = R″ = OCH2CF3 (2c)] in the presence or absence of AgOTf (OTf = CF3SO3) resulted in a rearrangement reaction to give the salts [R3P=N= PR′R″O-SiMe3]X (X = Br or OTf) ([4]X). Reaction of phosphine oxide 1a with the phosphoranimine BrPMe2=NSiPh3 (5) with a sterically encumbered silyl group also resulted in the analogous rearranged product [Me3P=N=PMe2O-SiPh3]X ([8]X) but at a significantly slower rate. In contrast, the direct reaction of the bulky tert-butyl substituted phosphine oxide, tBu3P=O (1b) with 2a or 2c in the presence of AgOTf yielded the phosphine oxide-stabilized phosphoranimine cations [tBu3P= O?PR′2=NSiMe3]+ ([3]+, R′ = Me (d), OCH2CF3 (e)). A mechanism is proposed for the unexpected formation of [4]+ in which the formation of the donor-stabilized adduct [3]+ occurs as the first step.
Spin chemistry of organometallic compounds 5. Interaction of N-bromohexamethyl disilazane with substituted silyl hydrides
Taraban, Marc B.,Rakhlin, Vladimir I.,Volkova, Olga S.,Podgorbunskaya, Tatyana A.,Kuibida, Leonid V.,Mirskov, Rudolf G.,Leshina, Tatyana V.,Sherstyannikova, Larisa V.,Voronkov, Mikhail G.
body text, p. 3815 - 3820 (2009/04/06)
Reaction of N-bromohexamethyl disilazane (Me3Si)2NBr with substituted triorganyl silanes R1R2R3SiH results in asymmetric disilazanes Me3SiNHSiR1R2R3 and bromination product, bromotrimethyl silane Me3SiBr. The reaction has demonstrated an unusual dependence on specific solvation. In benzene, bromination occurs immediately after mixing of the reagents, while in cyclohexane, the reaction products are formed only under UV-irradiation. Application of photoinduced CIDNP method has shown that the mechanism of bromination of triorganyl silanes is comprised of a series of consecutive radical stages involving N-centered disilazanyl (Me3Si)2N{radical dot} and Si-centered silyl R1R2R3Si{radical dot} radicals.
Reactions of N-bromohexamethyldisilazane with triorganylsilanes
Rakhlin,Podgorbunskaya,Mirskov,Voronkov,Gendin
, p. 1562 - 1563 (2008/02/07)
Reactions of N-bromohexamethyldisilazane (Me3Si)2NBr with Si-H compounds of the general formula RR'2SiH yield up to 90% of unsymmetrical disilazanes (Me3Si)2NSiRR2 and bromotrimethylsilane. An unexpected solvent effect on the reaction conditions is revealed: In benzene the products are formed already on mixing, whereas in cyclohexane, under UV irradiation only. Nauka/Interperiodica 2006.
