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Quintuple bond reactivity toward group 16 and 17 elements: addition vs insertion.

The low valent, coordinatively unsaturated, and formally quintuply bonded bimetallic aminopyridinato chromium complex 1 was investigated regarding its reactivity toward group 16 and 17 elements. Reaction of 1 with O(2) yielded a dimeric Cr oxo complex 2, a compound with a high formal oxidation state carrying both bridging and terminal oxo ligands. Reactions with the higher homologues of the group lead to the formation of dimeric Cr(II) complexes in which E(2)(2-) ligands were formed [E = S (3), Se (4), and Te (5)]. Here the quintuply bonded dichromium unit formally undergoes an addition reaction. Reaction of 1 with the homo diatomic molecules of the group 17 elements leads to products in which the Cr-Cr quintuple bond is inserted into the corresponding X(2) molecule [X = Cl (6), Br (7), and I (8)]. Complex 1 was also found to insert into the S-S and Se-Se bonds of 1,2-diphenyldisulfane or the corresponding selenium compound (complexes 9 and 10, respectively). All the compounds have been characterized by NMR and elemental analysis. Additionally, eight of the complexes have been characterized by X-ray analysis. The bimetallic Cr(II) complexes feature metal-metal distances between 1.8369(18) and 1.918(12) Å.