Quintuple Bond Reactivity toward Group 16 and 17 Elements: Addition vs Insertion

详细信息    查看全文

• 作者：Emmanuel Sobgwi Tamne ; Awal Noor ; Sadaf Qayyum ; Tobias Bauer ; Rhett Kempe
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：January 7, 2013
• 年：2013
• 卷：52
• 期：1
• 页码：329-336
• 全文大小：474K
• 年卷期：v.52,no.1(January 7, 2013)
• ISSN：1520-510X

文摘

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 O₂ 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 E₂^{2鈥?/sup> 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鈥揅r quintuple bond is inserted into the corresponding X₂ molecule [X = Cl (6), Br (7), and I (8)]. Complex 1 was also found to insert into the S鈥揝 and Se鈥揝e 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 CrII complexes feature metal鈥搈etal distances between 1.8369(18) and 1.918(12) 脜.}