Lehrstuhl Anorganische Chemie II, Universität Bayreuth, 95440 Bayreuth, Germany.
Inorg Chem. 2013 Jan 7;52(1):329-36. doi: 10.1021/ic3020805. Epub 2012 Dec 14.
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.
低价、配位不饱和、形式上五重键合的双金属氨基吡啶铬配合物 1 被研究了其对第 16 和 17 族元素的反应性。1 与 O(2)反应生成二聚 Cr 氧配合物 2，这是一种具有高形式氧化态的化合物，带有桥接和末端氧配体。与族中较高的同系物反应生成二聚 Cr(II)配合物，其中形成了 E(2)(2-)配体[E = S (3)、Se (4)和 Te (5)]。在这里，五重键合的二铬单元形式上经历了加成反应。1 与第 17 族元素的同原子双原子分子反应，导致产物中 Cr-Cr 五重键插入相应的 X(2)分子[X = Cl (6)、Br (7)和 I (8)]。配合物 1 也被发现插入 1,2-二苯二硫或相应的硒化合物（配合物 9 和 10）的 S-S 和 Se-Se 键中。所有化合物均通过 NMR 和元素分析进行了表征。此外，有 8 个配合物通过 X 射线分析进行了表征。双金属 Cr(II)配合物的金属-金属距离在 1.8369(18)和 1.918(12)Å 之间。
