Institut für Chemie, Abteilung Anorganische Chemie, Universität Rostock, Albert-Einstein-Strasse 3a, 18059 Rostock, Germany.
Inorg Chem. 2011 Mar 21;50(6):2691-702. doi: 10.1021/ic200005q. Epub 2011 Feb 22.
Differently substituted hydrazinophosphanes of the type (Me(3)Si)(2)N-N(SiMe(3))-PR(1)R(2) (R(1) = Cl with R(2) = Me, C(6)F(5) and R(1) = Me, R(2) = C(6)H(5)) have been studied in the reaction with Lewis acids such as ECl(3) (E = Al, Ga). For (Me(3)Si)(2)N-N(SiMe(3))-P(Cl)(Me) and (Me(3)Si)(2)N-N(SiMe(3))-P(Me)(C(6)H(5)), only adduct formation was found while a chlorine/methyl exchange reaction was observed for (Me(3)Si)(2)N-N(SiMe(3))-P(Cl)R (R = C(6)H(5) and C(6)F(5)) leading to the formation of (Me(2)ClSi)(Me(3)Si)N-N(SiMe(3))-P(Me)R, which crystallize as ECl(3) adducts. The free hydrazinophosphanes can be obtained by removal of the Lewis acid with the help of a strong base such as 4-(dimethylamino)pyridine (DMAP).
不同取代的腙基膦烷，如(Me(3)Si)(2)N-N(SiMe(3))-PR(1)R(2)（R(1) = Cl，R(2) = Me、C(6)F(5)和 R(1) = Me，R(2) = C(6)H(5))，与路易斯酸如 ECl(3)（E = Al、Ga）反应。对于(Me(3)Si)(2)N-N(SiMe(3))-P(Cl)(Me)和(Me(3)Si)(2)N-N(SiMe(3))-P(Me)(C(6)H(5))，只观察到加合物的形成，而对于(Me(3)Si)(2)N-N(SiMe(3))-P(Cl)R（R = C(6)H(5)和 C(6)F(5)），则观察到氯/甲基交换反应，导致形成(Me(2)ClSi)(Me(3)Si)N-N(SiMe(3))-P(Me)R，其结晶为 ECl(3)加合物。在强碱如 4-(二甲基氨基)吡啶（DMAP）的帮助下，可以通过去除路易斯酸来获得游离的腙基膦烷。
