Metaphosphorous acid (HOPO), a key intermediate in phosphorus chemistry, has been generated in syn- and anti-conformations in the gas phase by high-vacuum flash pyrolysis (HVFP) of a molecular precursor ethoxyphosphinidene oxide (EtOPO→C2 H4 +HOPO) at ca. 1000 K and subsequently trapped in an N2 -matrix at 2.8 K. Unlike the two conformers of the nitrogen analogue HONO, the anti-conformer of HOPO undergoes spontaneous rotamerization at 2.8 K via hydrogen-atom tunneling (HAT) with noticeable kinetic isotope effects for H/D (>104 for DOPO) and 16 O/18 O (1.19 for H18 OPO and 1.06 for HOP18 O) in N2 -matrices.
