The phosphinimines Ph3PNR (R = Ph 1, C6F52, tBu 3) are combined with B(C6F5)3 in an effort to explore the frustrated Lewis pair (FLP) chemistry. While compound 1 is shown to form an adduct with the borane, compounds 2 and 3 exhibit no apparent interaction. Nonetheless exposure of each of the three combinations to H2 resulted in the formation of the corresponding salts [Ph3PN(H)R][HB(C6F5)3] (R = Ph 5, C6F56, tBu 7). Reaction of 1 or 2 with B(C6F5)3 and carbon dioxide afforded Ph3PN(R)COOB(C6F5)3 (R = Ph 8, C6F59) while the corresponding reaction with 3 gave rise only to the tBuNCO and (Ph3PO)B(C6F5)3. Reactions of 1â3 and B(C6F5)3 with PhCCH proceeds to give either deprotonation or addition affording products of the form [Ph3PN(H)R][PhCCB(C6F5)3] or (Ph3PNR)(Ph)CCH(B(C6F5)3). The factors governing the nature of the dominant products are considered.
膦
酰亚胺 Ph3
PNR(R = Ph 1、 2、tBu 3)与 B(
C6F5)3 结合在一起,以探索受挫路易斯对(FLP)
化学。化合物 1 与
硼烷形成加合物,而化合物 2 和 3 则没有明显的相互作用。尽管如此,将这三种化合物中的每一种暴露于 H2 会形成相应的盐 [Ph3
PN(H)R][HB( )3](R = Ph 5、 6、tBu 7)。1 或 2 与 B( )3 和
二氧化碳反应生成 Ph3
PN(R)COOB( )3 (R = Ph 8、 9),而与 3 的相应反应只生成 tBuNCO 和 (Ph3PO)B( )3。1â3 和 B( )3 与 PhCCH 的反应要么发生去质子化反应,要么发生加成反应,生成 [Ph3
PN(H)R][PhCCB( )3] 或 (Ph3
PNR)(Ph)CCH(B( )3) 形式的产物。考虑了影响主要产物性质的因素。