Reactivity Studies on a Diazadiphosphapentalene.
The reactivity of diazadiphosphapentalene 1 towards various substrates was investigated. Reaction of 1 with ammonia-borane resulted in transfer hydrogenolysis concomitantly with the cleavage of a P-N bond. By treatment of 1 with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), oxidation took place at one of the phosphorus atoms of 1, and a P(V) /P(III) mixed-valence derivative was isolated. At the same time, it was demonstrated that only one of the phosphorus atoms in 1 behaves as an electron donor for electrophiles and Lewis acids. The former afforded an intramolecularly coordinated phosphine-phosphenium species, whereas the latter demonstrates the ligand property of 1. UV irradiation induced rearrangement of 1 into another example of another diazadiphosphapentalene.
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21, Singapore, 637371, Singapore.
Jingjing
J
Cui
NTU-CBC Crystallography Facility, Nanyang Technological University, Singapore.
Yongxin
Y
Li
NTU-CBC Crystallography Facility, Nanyang Technological University, Singapore.
Rakesh
R
Ganguly
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21, Singapore, 637371, Singapore. rkinjo@ntu.edu.sg.
Rei
R
Kinjo
Lewis acids; isomerization; organophosphorus compounds; oxidation; phosphorus