Yoon Joseph S, Abdellaoui Mehdi, Gembicky Milan, Bertrand Guy
UCSD-CNRS Joint Research Laboratory (IRL 3555), Department of Chemistry and Biochemistry, University of California San Diego La Jolla CA 92093-0358 USA
Chem Sci. 2024 Sep 2;15(38):15713-6. doi: 10.1039/d4sc05091f.
The reaction of the ,-diisopropyl bromoiminium salt with excess sodium phosphaethynolate (NaPCO) affords a diphospha-urea 2. Under blue light irradiation (450 nm), carbon monoxide is liberated affording the bis(carbene)P adduct 3. Photolysis of a benzene solution of 3 at 365 nm gives rise to the carbene dimer, namely the 1,2-bis(diisopropylamino)ethylene as a / mixture, along with white and red phosphorus. Under the same experimental conditions, but in the presence of excess 2,3-dimethyl-1,3-butadiene, the classical double Diels-Alder adduct of the triple-bonded diphosphorus P[triple bond, length as m-dash]P was obtained along with the bis(phospholene) formally resulting from a double [4 + 1] reaction of the diene with the bis(phosphinidene) form of P. A stepwise carbene-carbene exchange reaction also occurs between the monosubstituted aminocarbene of 3 and a cyclic (alkyl)(amino)carbene, possibly involving the transient formation of a diphosphorus analogue of a diazo compound.
α,β-二异丙基溴代亚胺鎓盐与过量的磷乙炔醇钠（NaPCO）反应得到二磷脲2。在蓝光照射（450 nm）下，释放出一氧化碳，得到双（卡宾）磷加合物3。3的苯溶液在365 nm处光解产生卡宾二聚体，即1,2-双（二异丙基氨基）乙烯，呈α/β混合物形式，同时还有白磷和红磷。在相同实验条件下，但在过量的2,3-二甲基-1,3-丁二烯存在下，除了由二烯与磷的双（磷烯）形式进行的双[4 + 1]反应正式生成的双（磷茂）外，还得到了三键双磷P≡P的经典双狄尔斯-阿尔德加合物。3的单取代氨基卡宾与环状（烷基）（氨基）卡宾之间也发生逐步的卡宾-卡宾交换反应，这可能涉及重氮化合物的二磷类似物的瞬时形成。
