Two simple acylnitrenes, 2-furoylnitrene (2) and 3-furoylnitrene (6), were generated through 266 nm laser photolysis of the corresponding azides. Both are magnetically bistable in cryogenic matrices, as evidenced by the direct observation of the closed-shell singlet state with IR spectroscopy in solid Ne, Ar, Kr, Xe, and N-2 matrices (3-40 K) and the triplet state in toluene (10 K) with EPR spectroscopy ((3)(2): |D/hc| = 1.48 cm ' and IE/hcl = 0.029 cm(-1); 3 6: |E/hc| = 1.39 cm-(1)and |D/hc|(c) = 0.039 cm(-1)).'Subsequent visible-light and UV laser irradiations led to the formation of furyl isocyanates (3 and 7) and ring-opening product 3-cyanoacrolein (9-E and 9-Z), respectively, in which the elusive 3-furylnitrene ((3)(8)) was also identified by IR and EPR spectroscopy |E/hc| = 1.12 cm(-1)and |E/hc| = 0.005 cm())(-1).