Abstract
Photolysis of red cis- and trans-[CrIII(cyclam)(N3)2](ClO4) (1a, 2a) (cyclam = 1,4,8,11-tetraazacyclotetradecane) in the solid state or aqueous solution by light affords the nitridochromium(V) complexes of cis- or trans-[CrV(N)(cyclam)(N3)](ClO4) (3a) and dinuclear [{trans-[CrV(N)(cyclam)]}2(μ-N3)](ClO4)3·3.5H2O (4a), respectively. 4a was converted to the bis(tetraphenylborate)−azide−2C2H5OH salt (4b). Crystallization of 4a from acetonitrileafter addition of AgClO4 and removal of AgN3yields octahedral trans-[CrV(N)(cyclam)(NCCH3)](ClO4)2 (5a). The crystal structures of 1a, 2b (which is the tetraphenylborate salt of 2a), 4a,b, 5a,b have been determined by single-crystal X-ray crystallography. All nitridochromium(V) compounds contain the trans-[CrV(N)(cyclam)]2+ fragment with an N⋮CrV moiety (1.56 ± 0.01 A). The electronic spectra of d1 configurated complexes display three low-intensity d−d bands which have been assigned in C4v symmetry as (xy) ((xz,yz) 2B2 → 2E, (xy) → (x2 − y2) 2B2 → 2B1, and (xy) → (z2) ...
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