5,5'-BI(1,3,2,4-DITHIADIAZOLYLIUM)(2+) BIS[HEXAFLUORO-ARSENATE(V)] - A GENERAL SYNTHETIC STRATEGY TO MOLECULES AND RADICALS CONTAINING THIAZYL RINGS

被引:17
作者
PARSONS, S [1 ]
PASSMORE, J [1 ]
WHITE, PS [1 ]
机构
[1] UNIV NEW BRUNSWICK, DEPT CHEM, FREDERICTON E3B 5A3, NB, CANADA
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1993年 / 10期
关键词
D O I
10.1039/dt9930001499
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The salt [SNS][AsF6] undergoes a quantitative multiple cycloaddition reaction with cyanogen to give the planar, centrosymmetric dication (CNSNS)22+, which has been characterised by vibrational and C-13 NMR spectroscopy, chemical analysis and X-ray crystallography. While the reaction between cyanogen and SNS+ must proceed via a 1 : 1 cycloadduct, NCCNSNS+, this was not prepared or observed. The cycloaddition of SNS + to NCCNSNS+ must therefore be kinetically preferred, contrary to arguments based on simple frontier molecular orbital (FMO) theory. By contrast, the reaction of [SNS][AsF6] with [N=CCNSNSCH][AsF6]to give [HCSNSC-CNSNS][AsF6]2 was complete only after 10 weeks at 50-degrees-C, in complete accord with FMO theory. These results are rationalised in terms of the influence of high-energy, in-plane molecular orbitals and the electrostatic interaction between SNS+ and the slightly negatively charged nitrogen atom (N) in the CNSNS+ ring, which facilitates the second cycloaddition. The salt [(CNSNS)2][AsF6]2 potentially provides access to a new family of eight other bicyclic CNS dications, radical cations and diradicals, of which .SNSNC-CNSNS+, +SNSNC-CNSSN. and +NSSNC-CNSNS+ are reported.
引用
收藏
页码:1499 / 1507
页数:9
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