Rearrangements of acyl, thioacyl, and imidoyl (thio)cyanates to iso(thio)cyanates, acyl iso(thio)cyanates to (thio)acyl isocyanates, and imidoyl iso(thio)cyanates to (thio)acyl carbodiimides, RCX-YCN ⇌ RCX-NCY ⇌ RCY-NCX ⇌ RCY-XCN (X and Y = O, S, NR').

Two types of rearrangements have been investigated computationally at the B3LYP/6-311+G(d,p) level. The activation barriers for rearrangement of acyl thiocyanates RCO-SCN to the corresponding isothiocyanates RCO-NCS are 30-31 kcal/mol in agreement with the observation that the thiocyanates are in some cases isolable albeit very sensitive compounds. Alkoxycarbonyl-, (alkylthio)carbonyl- and carbamoyl thiocyanates are isolable and have higher calculated barriers (ca. 40 kcal/mol) toward rearrangement to isothiocyanates, whereas all thioacyl thiocyanate derivatives are rather unstable compounds with barriers in the range 20-30 kcal/mol for rearrangement to the isothiocyanates. Acyl-, alkoxycarbonyl-, and carbamoyl cyanates R-CO-OCN are predicted to be in some cases isolable compounds with barriers up to ca. 40 kcal/mol for rearrangement to the isocyanates RCO-NCO. All of the rearrangements of this type involve the HOMO of a nearly linear (thio)cyanate anion and the LUMO of the acyl cation, in particular the acyl C═X π* orbital. The second type of rearrangement involves 1,3-shifts of the groups R attached to the (thio)acyl groups, that is, acyl isothiocyanate-thioacyl isocyanate and imidoyl isothiocyanate-thioacyl carbodiimide rearrangements. These reactions involve four-membered cyclic, zwitterionic transition states facilitated by lone pair-LUMO interactions between the migrating R group and the neighboring iso(thio)cyanate function. Combination of the two rearrangements leads to the general reaction scheme RCX-YCN ⇌ RCX-NCY ⇌ RCY-NCX ⇌ RCY-XCN (X and Y = O, S, NR').