提出了一种简便有效地合成3H-磷杂戊烯的方法,R-P = C = C(H)-R',包括用二烷基铝氢化物处理二炔基膦(加氢铝化)和从中间烯基-炔基膦中消除铝炔基。磷杂芳烃的稳定性取决于在磷(芳基或CH(SiMe 3)2基团)上的取代基的空间屏蔽作用。仅超甲磺胺化合物在室温下在溶液中持久存在。这种简单的方法从容易获得的二炔基膦和市售氢化铝(HAlEt 2,HAl i Bu 2)允许生成过渡物种,这些过渡物种通过与过渡金属的配位而被捕获。在η 1经由P-W线键-coordination观察到钨,而经由P侧上协调= C键导致与铂。均三甲苯基衍生物的分解产生了前所未有的产物,其可能是由1,3-H移至P原子,第二磷杂芳烃的P = C键进行氢磷酸化以及形成P-P键形成的。
提出了一种简便有效地合成3H-磷杂戊烯的方法,R-P = C = C(H)-R',包括用二烷基铝氢化物处理二炔基膦(加氢铝化)和从中间烯基-炔基膦中消除铝炔基。磷杂芳烃的稳定性取决于在磷(芳基或CH(SiMe 3)2基团)上的取代基的空间屏蔽作用。仅超甲磺胺化合物在室温下在溶液中持久存在。这种简单的方法从容易获得的二炔基膦和市售氢化铝(HAlEt 2,HAl i Bu 2)允许生成过渡物种,这些过渡物种通过与过渡金属的配位而被捕获。在η 1经由P-W线键-coordination观察到钨,而经由P侧上协调= C键导致与铂。均三甲苯基衍生物的分解产生了前所未有的产物,其可能是由1,3-H移至P原子,第二磷杂芳烃的P = C键进行氢磷酸化以及形成P-P键形成的。
作者:Robert Choukroun、Yannick Miquel、Bruno Donnadieu、Alain Igau、Claudine Blandy、Jean Pierre Majoral
DOI:10.1021/om980983x
日期:1999.4.1
Treatment of the bis(alkynyl)phosphane Ar−P(C⋮CPh)2 (3) (Ar = 2,4,6-t-Bu3C6H2) with Cp2V gives the vanadacyclopropene phosphane 5, which was characterized by X-ray diffraction. The reactivity of 5 toward HCl in THF or toluene gives 3 or the alkenyl alkynyl phosphane (E/Z isomers) isolated as its sulfur analogue (PhCHCH)(PhC⋮C)PAr(S).
用Cp 2 V处理双(炔基)膦Ar-P(C⋮CPh)2(3)(Ar = 2,4,6- t -Bu 3 C 6 H 2),得到钒环丙烷膦5,为由X射线衍射表征。5在THF或甲苯中对HCl的反应活性得到3或作为硫类似物(PhCH CH)(PhC⋮C)PAr(S)分离的烯基炔基膦(E / Z异构体)。
Versatile Behavior of a New Class of Bicyclic Compounds: Zirconacyclopentadiene Phosphiranes
Diacetylenic phosphanes are cleanly transformed when reacted with zirconocene into zirconacyclopentadiene phosphiranes. These new cyclic systems are the source of a variety of unsaturated phosphorus compounds like phospharadialene or alkenyl alkynyl phosphanes.
3H‐Phosphaallenes Revisited: Facile Synthesis by Hydroalumination of Alkynylphosphines and β‐Elimination, Stability and Trapping of Transient Species by Coordination to Transition Metal Atoms
作者:Hans Klöcker、Jonas C. Tendyck、Lukas Keweloh、Alexander Hepp、Werner Uhl
DOI:10.1002/chem.201806334
日期:2019.3.27
starting with easily accessible dialkynylphosphines and commercially available aluminiumhydrides (HAlEt2, HAliBu2) allows the generation of transient species, which were trapped by coordination to transition metals. The η1‐coordination via a P−W bond was observed for tungsten, while the side‐on coordination via the P=C bond resulted with platinum. Decomposition of the mesityl derivative yielded an unprecedented
提出了一种简便有效地合成3H-磷杂戊烯的方法,R-P = C = C(H)-R',包括用二烷基铝氢化物处理二炔基膦(加氢铝化)和从中间烯基-炔基膦中消除铝炔基。磷杂芳烃的稳定性取决于在磷(芳基或CH(SiMe 3)2基团)上的取代基的空间屏蔽作用。仅超甲磺胺化合物在室温下在溶液中持久存在。这种简单的方法从容易获得的二炔基膦和市售氢化铝(HAlEt 2,HAl i Bu 2)允许生成过渡物种,这些过渡物种通过与过渡金属的配位而被捕获。在η 1经由P-W线键-coordination观察到钨,而经由P侧上协调= C键导致与铂。均三甲苯基衍生物的分解产生了前所未有的产物,其可能是由1,3-H移至P原子,第二磷杂芳烃的P = C键进行氢磷酸化以及形成P-P键形成的。