NDLI: Reactions at the Ru-S bonds of coordinatively unsaturated ruthenium complexes with tethered 2,6-dimesitylphenyl thiolate.

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Reactions at the Ru-S bonds of coordinatively unsaturated ruthenium complexes with tethered 2,6-dimesitylphenyl thiolate.

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Ohki, Yasuhiro Takikawa, Yuko Sadohara, Hitomi Kesenheimer, Christian Engendahl, Barthel Kapatina, Elissavet Tatsumi, Kazuyuki
Description	Country affiliation: Japan Author Affiliation: Ohki Y ( Department of Chemistry, Graduate School of Science and Research Center for Materials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan. i45100a@nucc.cc.nagoya-u.ac.jp)
Abstract	Coordinatively unsaturated ruthenium complexes with a tethered SDmp (Dmp=2,6-dimesitylphenyl) ligand, [(DmpS)Ru(PR(3))][BAr(F) (4)] (3 a: R=Et; 3 b: R=Ph; Ar(F)=3,5-(CF(3))(2)C(6)H(3)), were synthesized by the reactions of [{(p-cymene)RuCl}(2)(mu-Cl)(2)], LiSDmp, phosphines, and NaBAr(F) (4). The Ru--S bonds in 3 a and 3 b were found to serve as the polarized reactive site in reactions with alkyl halides, diazoalkanes, (p-tosyliminoiodo)benzene, phenylacetylene, and H(2). Alkylation of 3 a and 3 b with methyl iodide or ethyl bromide occurred instantaneously to give the thioether complexes [(DmpSR')RuX(PR(3))][BAr(F) (4)] (4 a: R=Et, R'=Me, X=I; 4 b: R=R'=Et, X=Br; 4 c: R=Ph, R'=Me, X=I; 4 d: R=Ph, R'=Et, X=Br). Treatment of 3 a with diazoalkanes N(2)CHR (R=CO(2)Et, SiMe(3)) led to the cycloaddition of carbenes to the Ru--S bond to form [DmpS(CHR)Ru(PEt(3))][BAr(F) (4)] (5 a: R=CO(2)Et; 5 b: R=SiMe(3)), whereas the reaction with (p-tosyliminoiodo)benzene gave rise to [DmpS{NS(O)(C(6)H(4)-4-CH(3))O}Ru(PEt(3))][BAr(F) (4)] (6), which contains a five-membered ruthenacycle of RuSNSO. Addition of phenylacetylene to the Ru--S bond occurred reversibly to produce the vinyl sulfide complexes [DmpS(PhCCH)Ru(PR(3))][BAr(F) (4)] (7 a: R=Et; 7 b: R=Ph). On the other hand, the phenylacetylene at ruthenium slowly isomerized to vinylidene and bridged Ru and S in the products, [DmpS{C(CHPh)}Ru(PR(3))][BAr(F) (4)] (8 a: R=Et; 8 b: R=Ph). Complex 3 a catalyzed the hydrogenation of acetophenone, in which the heterolytic H-H splitting at the Ru-S site is suggested to be involved in the mechanism.
File Format	HTM / HTML
ISSN	18614728
Issue Number	8-9
Journal	Chemistry - An Asian Journal
Volume Number	3
e-ISSN	1861471X
Language	English
Publisher	Wiley-VCH
Publisher Date	2008-09-01
Publisher Place	Germany
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Discipline Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Biochemistry

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Reactions at the Ru-S bonds of coordinatively unsaturated ruthenium complexes with tethered 2,6-dimesitylphenyl thiolate.

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