Reaction of a (salen)ruthenium(VI) nitrido complex with thiols. C-H bond activation by (salen)ruthenium(IV) sulfilamido species

Wai Lun Man, William W.Y. Lam, Hoi Ki Kwong, Shie Ming Peng, Wing Tak Wong, Tai Chu Lau

Research output: Journal article publicationJournal articleAcademic researchpeer-review

27 Citations (Scopus)

Abstract

The reaction of [RuvI(N)(L)(MeOH)](PF6) [1; L = N,N′-bis(salicylidene)-o-cyclohexyldiamine dianion] with a stoichiometric amount of RSH in CH3CN gives the corresponding (salen)ruthenium(IV) sulfilamido species [RuIv{N(H)SR}(L)(NCCH3)](PF 6) (2a, R = tBu; 2b, R = Ph). Metathesis of 2a with NaN3 in methanol affords [RuIv{N(H)StBu}(L) (N3)l (2c). 2a undergoes further reaction with 1 equiv of RSH to afford a (salen)ruthenium(lll) sulfilamine species, [Ru111HN(H) 2StBU}(L)(NCCH3)](PF6) (3). On the other hand, 2b reacts with 2 equiv of PhSH to give a (salen)ruthenium(lll) ammine species [Ru111 (NH3)(L)(NCCH3)[PF 6) (4); this species can also be prepared by treatment of 1 with 3 equiv of PhSH. The X-ray structures of 2c and 4 have been determined. Kinetic studies of the reaction of 1 with excess RSH indicate the following schemes: 1 → 2a → 3 (R = tBu), 1 →2b →* 4 (R = Ph). The conversion of 1 to 2 probably involves nucleophilic attack of RSH at the nitrido ligand, followed by a proton shift. The conversions of 2a to 3 and 2b to 4 are proposed to involve rate-limiting H-atom abstraction from RSH by 2a or 2b. 2a and 2b are also able to abstract H atoms from hydrocarbons with weak C-H bonds. These reactions occur with large deuterium isotope effects; the kinetic isotope effect values for the oxidation of 9,10-dihydroanthracene, 1,4cyclohexadiene, and fluorene by 2a are 51,56, and 11, respectively.
Original languageEnglish
Pages (from-to)73-81
Number of pages9
JournalInorganic Chemistry
Volume49
Issue number1
DOIs
Publication statusPublished - 4 Jan 2010
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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