Nitrogen-Phosphorus(III)-Chalcogen Macrocycles for the Synthesis of Polynuclear Silver(I) Sandwich Complexes

作者：Yogendra Sivathmeehan; Hennersdorf Felix; Weigand Jan J^*

来源：Inorganic Chemistry, 2017, 56(15): 8698-8704.

DOI：10.1021/acs.inorgchem.7b00141

The synthesis of inorganic N-P(III)-Ch-based macrocycles [-PhP-NMe-PPh-Ch-](2) (8(ch); Ch = S, Se) is presented by incorporating two nitrogen, two chalcogen, and four phosphorus atoms. The macrocycles are conveniently obtained via the cyclocondensation reaction of Na(2)Ch (Ch = S, Se) with the acyclic dichlorodiphosphazane ClPhP-NMe-PCIPh (9). Treatment with elemental sulfur (S-8) or gray selenium (Se-gray) results in an oxidative ring contraction to give 1,3,2,4-thiazadiphosphetidine 2,4-disulfide (10(s)) and 1,3,2,4-selenazadiphosphetidine 2,4-diselenide (10(s)), respectively. Macrocycles 8(ch) are excellent multidentate ligands for transition metal complexation, as demonstrated by the isolation of mono-, di- tri-, and tetranuclear silver sandwich complexes. The polynuclear silver complexes are comprehensively characterized, including detailed NMR and X-ray analysis.

• 出版日期2017-8-7