Metal-free σ-bond metathesis in ammonia activation by a diazadiphosphapentalene.
A diazadiphosphapentalene derivative 5 featuring a bent geometry with two phosphorus atoms at the bridgehead has been synthesized. Under mild conditions, compound 5 readily activated ammonia to afford 1-aza-2,3-diphospholene derivative 6 bearing an enamine group. The reaction is therefore viewed as a formal σ-bond metathesis between an N-H bond of ammonia and an endocyclic P-N bond of 5. Details of the reaction mechanism for ammonia activation as well as subsequent isomerization were explored by density functional theory calculations.
Division of Chemistry & Biological Chemistry, School of Physical & Mathematical Sciences, and ‡NTU-CBC Crystallography Facility, Nanyang Technological University , Singapore 637371, Singapore.
Jingjing
J
Cui
Yongxin
Y
Li
Rakesh
R
Ganguly
Anusiya
A
Inthirarajah
Hajime
H
Hirao
Rei
R
Kinjo