An atom-economical synthesis of arsaalkenes via a net coupling of aryl arsines with aryl or alkyl isocyanides at zirconium is presented. Reaction of zirconium arsenido complexes (N3N)ZrAsHAr [N3N = N(CH2CH2NSiMe3)3(3-); Ar = Ph, (2) Mes (3)] with aryl and alkyl isocyanides yields arsaalkene products of the general form (N3N)Zr[NRC(H)═As(Ar)]. Two examples (5: R = Mes, Ar = Ph; 6: R = CH2Ph, Ar = Mes) were structurally characterized. Observation of intermediates in the reaction and structural characterization of the previously reported 1,1-insertion product benzylisocyanide with (N3N)ZrAsPh2 (8), (N3N)Zr[η(2)-C(PPh2)=NCH2Ph] (9), support the mechanistic hypothesis that these reactions occur via 1,1-insertion followed by rearrangement.
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