Novel N-phosphinoguanidines (HNiPr)(Ph2PNiPr)C(NAr) (Ar = 2,6-iPr2C6H3, 2,4,6-Me3C6H2) react with AlMe3 to afford phosphinimine-amidinato derivatives, via an unprecedented rearrangement of an initial N-phosphinoguanidinato intermediate. A reasonable mechanism has been proposed for this transformation, supported by DFT calculations, involving carbodiimide de-insertion followed by a [3+2] cycloaddition.
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