The photochemistry of the a-diazo sulfoxide 7 has been investigated in solid argon at 10 K by IR spectroscopy. The sulfinyl carbene was not detected directly but instead underwent photochemically induced hetero-Wolff rearrangement to the sulfine 8 which could be detected and characterized following irradiation at 248 nm. Further photochemical reaction of this intermediate led to the oxathiirane 9 which was most readily detected on irradiation of 7 at 308 nm. The matrix-isolated species were identified by comparison of experimental and calculated IR spectra. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)