The action of SOX2 or (COX)2 on oxovanadium(1V) porphyrin complexes [V'vL(0)] (L = porphyrinate) under mild conditions affords the corresponding dihalogenovanadium(1V) porphyrins [VIVLX2] (X = CI or Br). These very reactive complexes are remarkable precursors to low-valent vanadium porphyrins. Extended X-ray absorption fine structure spectroscopy at the Br K edge confirms the trans configuration and lNDO/S calculations suggest that the absence of an e.s.r. signal is due to an orbitally degenerate ground state.
Die Behandlung der Oxoporphyrinato‐V(IV)‐Komplexe (I) mit Thionyl‐ oder Oxalylchlo‐ 134 rid bzw. ‐bromid führt zu den Dihalogeno‐V(IV)‐Derivaten (II), die aufgrund ihrer großen Reaktivität bemerkenswerte Vorläufer für niedrig‐wertige V‐porphyrine sind.
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