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Transformation of Open-Chain Thioether–Dithiolato to Cyclic Thioether Ligands by CS Bond Cleavage and Bond Formation at Ruthenium Centers: Synthesis of the Trithiobenzo[9]crown-3 Complex [Ru(Bzo-9S3)(CO)Br2]

✍ Scribed by Prof. Dr. Dieter Sellmann; Dr. Falk Knoch; Christina Wronna


Publisher
John Wiley and Sons
Year
1988
Tongue
English
Weight
262 KB
Volume
27
Category
Article
ISSN
0044-8249

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✦ Synopsis


Reaction of 2 with CO in the presence of nBuLi: 2 (200 mg, 0.22 mmol) in THF (30 mL) was treated at -78°C with 0.3 mL (0.48 mmol) of an nBuLi solution (1.6 M in hexane). The deeo red solution was stirred under CO for 10 min at room temperature and then treated with 5 mL of MeOH After evaporation of the solvents, the products 3 and 4 were identilied by IR and mass spectroscopy (see [3]). Deuteration of 2 : 2 (45 mg, 0.05 mmol) in T H F (20 mL) was treated at -78°C with 0.063 mL (0.1 mmol) of an nBuLi solution (1.6 M in hexane) and warmed u p to room temperature. After hydrolysis with several drops of D20. the solvents were evaporated. The residue was dissolved in CH2CI,. the solution was filtered, and the CH2C12 was evaporated. 1R: vN.,,=2415 cm-I. 5 : 2 (400 mg, 0.44 mmol) in T H F (40 mL) was treated with Me1 ( I mL, 16 mrnol). After stirring for 3 h at room temperature, the precipitated, beige 5 (444 mg = 97% crude product) was separated, dissolved in CH2C12. and induced to crystallize by addition of a layer of MeOH at room temperature. Yield 295 mg (64%) 5 .