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λ 3 ‐Pyrroloazaphosphinines with Relatively Stable P=C Double Bonds
Author(s) -
Huang Haiyang,
Wei Zhibin,
Hou Jingjing,
Wang Ruoqing,
Tao Guanyu,
Wang Mincan,
Duan Zheng,
Mathey François
Publication year - 2018
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201800492
Subject(s) - chemistry , antiparallel (mathematics) , double bond , delocalized electron , ring (chemistry) , ligand (biochemistry) , molecule , stereochemistry , crystallography , polymer chemistry , organic chemistry , receptor , biochemistry , physics , quantum mechanics , magnetic field
The first pyrroloazaphosphinines with nitrogen at the junction, 7a and 7b , have been prepared by a special route involving the collapse of the phosphorus bridges of appropriate 7‐phosphanorbornenes. The parent molecule 7a has a strictly planar azaphosphinine ring with some electronic delocalization according to DFT computations. Its P=C double bond does not react with 2,3‐dimethylbutadiene unless P is coordinated to Mo(CO) 5 . Compound 7a reacts with Cu I to give a new type of polymeric complex [–Cu‐µ 2 ‐ 7a –] n in which P acts as a bridging ligand and the ligand planes are antiparallel. The benzo‐annulated and bromo‐substituted 7b displays a skewed ring according to DFT computations and its P=C double bond is reactive toward 2,3‐dimethylbutadiene without complexation.