Hansmann Max M, Ruiz David A, Liu Liu Leo, Jazzar Rodolphe, Bertrand Guy
UCSD-CNRS Joint Research Chemistry Laboratory (UMI 3555) , Department of Chemistry , University of California San Diego , La Jolla , CA 92093-0343 , USA . Email:
Chem Sci. 2017 May 1;8(5):3720-3725. doi: 10.1039/c7sc00300e. Epub 2017 Mar 8.
Although BH simply coordinates the endocyclic P of (phospholidino)phosphaketene , the bulkier B(CF) gives rise to a zwitterionic diphosphirenium, which is a novel type of 2π-electron aromatic system as shown by the calculated NICS values. While the reaction of with Na[PCO(dioxane) ] is unselective, the same reaction with the sterically bulky (phospholidino)phosphaketene [Ar** = 2,6-bis[di(4--butylphenyl)methyl]-4-methylphenyl selectively affords a sodium bridged dimer containing a hitherto unknown λ,λ,λ-triphosphete core. The latter formally results from "P" addition to a 1,3-P/C-dipole. Similarly, adamantyl isonitrile adds to giving a 4-membered phosphacycle. In contrast to , the phosphaketene derived from the electrophilic diazaphospholidine-4,5-dione is unstable and reacts with a second molecule of Na[PCO(dioxane) ] to afford a 1,3,4-oxadiphospholonide derivative.
尽管BH仅配位（磷环丁烷）磷杂乙酮的内环磷原子，但体积更大的B(CF)会生成两性离子二磷烯鎓，如计算出的核独立化学位移（NICS）值所示，它是一种新型的2π电子芳香体系。虽然 与Na[PCO(二氧六环) ]的反应没有选择性，但与空间位阻较大的（磷环丁烷）磷杂乙酮 [Ar** = 2,6-双[二(4-叔丁基苯基)甲基]-4-甲基苯基] 的相同反应选择性地提供了一种含有迄今未知的λ,λ,λ-三磷环丁烷核心的钠桥联二聚体。后者正式源于“P”加成到一个1,3-P/C偶极体上。类似地，金刚烷基异腈加成到 上生成一个四元磷环。与 相反，由亲电重氮磷环丁烷-4,5-二酮衍生的磷杂乙酮不稳定，会与第二个Na[PCO(二氧六环) ]分子反应，得到一种1,3,4-氧杂二磷杂环戊烯酮衍生物。
