Abstract
The chemistry of ruthenium pinacolate complexes has not been well explored. In this work, ruthenium(VI) nitrido perfluoropinacolate (pinF) complexes have been synthesized and their reactivity has been investigated. Treatment of (nBu4N)[Ru(N)Cl4] with Na2pinF afforded (nBu4N)[Ru(N)(pinF)Cl2] (1) that has been used as a starting material for synthesis of Ru(pinF) complexes. Chloride substitution of 1 with K[N(Ph2PQ)2] and Na(LOEt) (LOEt− = [Co(η5-C5H5){P(O)(OEt)2}3]−) afforded [Ru(N)(pinF){N(Ph2PQ)2}] (Q = S (2), Se (3)) and [(LOEt)Ru(N)(pinF)] (4), respectively. Nucleophilic attack of 4 with PPh3 and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (ImDipp) gave the Ru(IV) phosphoraneiminate [(LOEt)Ru(NPPh3)(pinF)] (5) and imidazolin-2-iminate [(LOEt)Ru(NImDipp)(pinF)] (6) complexes, respectively. The dichloride analogue of 5, [(LOEt)Ru(NImDipp)Cl2] (7), has been synthesized and structurally characterized. Oxidation of 7 with NR3SbCl6 (R = 4-bromophenyl) gave [LOEtRuCl3]SbCl6 that was co-crystallized with NHImDipp. The crystal structures of 1, 2, 4, 5 and 7 have been determined.
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