C-H cleavage and double alkyl additions to the disulfido ligand in dicyanido-bridged Ru2S2 complexes

Sumito Ishizu; Hiroyasu Sugiyama; Brian K. Breedlove; Kazuko Matsumoto

doi:10.1021/ic062460k

C-H cleavage and double alkyl additions to the disulfido ligand in dicyanido-bridged Ru₂S₂ complexes

Sumito Ishizu, Hiroyasu Sugiyama, Brian K. Breedlove, Kazuko Matsumoto

SCI - Chemistry

Waseda University

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

Abstract

Novel dicyanido-bridged dicationic Ru^IIISSRu^III complexes [{Ru(P(OCH₃)₃)₂}₂(μ- S₂)(μ-X)₂{μ-m-C₆H₄(CH ₂CN)₂}]-(CF₃SO₃)₂ (4, X = Cl, Br) were synthesized by the abstraction of the two terminal halide ions of [{RuX(P(OCH₃)₃)₂}^2- (μ-S ₂)(μ-X)₂] (1, X = Cl, Br) followed by treatment with m-xylylenedicyanide. 4 reacted with 2,3-dimethylbutadiene to give the C ₄S₂ ring-bridged complex [{Ru(P(OCH₃) ₃)₂}₂{μ-SCH₂C(CH ₃)=C(CH₃)CH₂S}(μ-X)₂{μ-m- C₆H₄(CH₂-CN)₂}](CF ₃SO₃)₂ (6, X = Cl, Br). In addition, 4 reacted with 1-alkenes in CH₃OH to give alkenyl disulfide complexes [{Ru(P(OCH₃)₃)₂}₂{μ-SS(CH ₂C=CHR)}(μ-Cl)₂-{μ-m-C₆H ₄(CH₂CN)₂}](CF₃SO₃) (7: R = CH₂CH₃, 9: R = CH₂-CH₂CH ₃) and alkenyl methyl disulfide complexes [{Ru(P(OCH ₃)₃)₂}₂{μ-S(CH ₃)S(CH₂C=HR)}(μ-Cl)₂{μ-m-C ₆H₄(CH₂-CN)₂}](CF₃SO ₃)₂ (8: R = CH₂CH₃,10: R = CH ₂CH₂CH₃) via the activation of an allylic C-H bond followed by the elimination of H⁺ or condensation with CH ₃OH. Additionally, the reaction of 4 with 3-penten-1-ol gave [{Ru-(P(OCH₃)₃)₂}₂{μ-SS(CH ₂C=CHCH₂OH)}(μ-Cl)₂{μ-m-C ₆H₄(CH₂CN)₂}](CF₃SO ₃) (11) via the elimination of H⁺ and [{Ru(P(OCH ₃)₃)₂}₂(μ-SCH₂CH= CHCH₂S)(μ-Cl)₂{μ-m-C₆H ₄(CH₂CN)₂}](CF₃SO₃) ₂ (12) via the intramolecular elimination of a H₂O molecule. 12 was exclusively obtained from the reaction of 4 with 4-bromo-1-butene.

Original language	English
Pages (from-to)	3726-3735
Number of pages	10
Journal	Inorganic Chemistry
Volume	46
Issue number	9
DOIs	https://doi.org/10.1021/ic062460k
Publication status	Published - 2007 Apr 30

Access to Document

10.1021/ic062460k

Cite this

@article{2dfe846ea9aa4a95ab60198e0b830a93,

title = "C-H cleavage and double alkyl additions to the disulfido ligand in dicyanido-bridged Ru2S2 complexes",

abstract = "Novel dicyanido-bridged dicationic RuIIISSRuIII complexes [{Ru(P(OCH3)3)2}2(μ- S2)(μ-X)2{μ-m-C6H4(CH 2CN)2}]-(CF3SO3)2 (4, X = Cl, Br) were synthesized by the abstraction of the two terminal halide ions of [{RuX(P(OCH3)3)2}2- (μ-S 2)(μ-X)2] (1, X = Cl, Br) followed by treatment with m-xylylenedicyanide. 4 reacted with 2,3-dimethylbutadiene to give the C 4S2 ring-bridged complex [{Ru(P(OCH3) 3)2}2{μ-SCH2C(CH 3)=C(CH3)CH2S}(μ-X)2{μ-m- C6H4(CH2-CN)2}](CF 3SO3)2 (6, X = Cl, Br). In addition, 4 reacted with 1-alkenes in CH3OH to give alkenyl disulfide complexes [{Ru(P(OCH3)3)2}2{μ-SS(CH 2C=CHR)}(μ-Cl)2-{μ-m-C6H 4(CH2CN)2}](CF3SO3) (7: R = CH2CH3, 9: R = CH2-CH2CH 3) and alkenyl methyl disulfide complexes [{Ru(P(OCH 3)3)2}2{μ-S(CH 3)S(CH2C=HR)}(μ-Cl)2{μ-m-C 6H4(CH2-CN)2}](CF3SO 3)2 (8: R = CH2CH3,10: R = CH 2CH2CH3) via the activation of an allylic C-H bond followed by the elimination of H+ or condensation with CH 3OH. Additionally, the reaction of 4 with 3-penten-1-ol gave [{Ru-(P(OCH3)3)2}2{μ-SS(CH 2C=CHCH2OH)}(μ-Cl)2{μ-m-C 6H4(CH2CN)2}](CF3SO 3) (11) via the elimination of H+ and [{Ru(P(OCH 3)3)2}2(μ-SCH2CH= CHCH2S)(μ-Cl)2{μ-m-C6H 4(CH2CN)2}](CF3SO3) 2 (12) via the intramolecular elimination of a H2O molecule. 12 was exclusively obtained from the reaction of 4 with 4-bromo-1-butene.",

author = "Sumito Ishizu and Hiroyasu Sugiyama and Breedlove, {Brian K.} and Kazuko Matsumoto",

year = "2007",

month = apr,

day = "30",

doi = "10.1021/ic062460k",

language = "English",

volume = "46",

pages = "3726--3735",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "9",

}

TY - JOUR

T1 - C-H cleavage and double alkyl additions to the disulfido ligand in dicyanido-bridged Ru2S2 complexes

AU - Ishizu, Sumito

AU - Sugiyama, Hiroyasu

AU - Breedlove, Brian K.

AU - Matsumoto, Kazuko

PY - 2007/4/30

Y1 - 2007/4/30

N2 - Novel dicyanido-bridged dicationic RuIIISSRuIII complexes [{Ru(P(OCH3)3)2}2(μ- S2)(μ-X)2{μ-m-C6H4(CH 2CN)2}]-(CF3SO3)2 (4, X = Cl, Br) were synthesized by the abstraction of the two terminal halide ions of [{RuX(P(OCH3)3)2}2- (μ-S 2)(μ-X)2] (1, X = Cl, Br) followed by treatment with m-xylylenedicyanide. 4 reacted with 2,3-dimethylbutadiene to give the C 4S2 ring-bridged complex [{Ru(P(OCH3) 3)2}2{μ-SCH2C(CH 3)=C(CH3)CH2S}(μ-X)2{μ-m- C6H4(CH2-CN)2}](CF 3SO3)2 (6, X = Cl, Br). In addition, 4 reacted with 1-alkenes in CH3OH to give alkenyl disulfide complexes [{Ru(P(OCH3)3)2}2{μ-SS(CH 2C=CHR)}(μ-Cl)2-{μ-m-C6H 4(CH2CN)2}](CF3SO3) (7: R = CH2CH3, 9: R = CH2-CH2CH 3) and alkenyl methyl disulfide complexes [{Ru(P(OCH 3)3)2}2{μ-S(CH 3)S(CH2C=HR)}(μ-Cl)2{μ-m-C 6H4(CH2-CN)2}](CF3SO 3)2 (8: R = CH2CH3,10: R = CH 2CH2CH3) via the activation of an allylic C-H bond followed by the elimination of H+ or condensation with CH 3OH. Additionally, the reaction of 4 with 3-penten-1-ol gave [{Ru-(P(OCH3)3)2}2{μ-SS(CH 2C=CHCH2OH)}(μ-Cl)2{μ-m-C 6H4(CH2CN)2}](CF3SO 3) (11) via the elimination of H+ and [{Ru(P(OCH 3)3)2}2(μ-SCH2CH= CHCH2S)(μ-Cl)2{μ-m-C6H 4(CH2CN)2}](CF3SO3) 2 (12) via the intramolecular elimination of a H2O molecule. 12 was exclusively obtained from the reaction of 4 with 4-bromo-1-butene.

AB - Novel dicyanido-bridged dicationic RuIIISSRuIII complexes [{Ru(P(OCH3)3)2}2(μ- S2)(μ-X)2{μ-m-C6H4(CH 2CN)2}]-(CF3SO3)2 (4, X = Cl, Br) were synthesized by the abstraction of the two terminal halide ions of [{RuX(P(OCH3)3)2}2- (μ-S 2)(μ-X)2] (1, X = Cl, Br) followed by treatment with m-xylylenedicyanide. 4 reacted with 2,3-dimethylbutadiene to give the C 4S2 ring-bridged complex [{Ru(P(OCH3) 3)2}2{μ-SCH2C(CH 3)=C(CH3)CH2S}(μ-X)2{μ-m- C6H4(CH2-CN)2}](CF 3SO3)2 (6, X = Cl, Br). In addition, 4 reacted with 1-alkenes in CH3OH to give alkenyl disulfide complexes [{Ru(P(OCH3)3)2}2{μ-SS(CH 2C=CHR)}(μ-Cl)2-{μ-m-C6H 4(CH2CN)2}](CF3SO3) (7: R = CH2CH3, 9: R = CH2-CH2CH 3) and alkenyl methyl disulfide complexes [{Ru(P(OCH 3)3)2}2{μ-S(CH 3)S(CH2C=HR)}(μ-Cl)2{μ-m-C 6H4(CH2-CN)2}](CF3SO 3)2 (8: R = CH2CH3,10: R = CH 2CH2CH3) via the activation of an allylic C-H bond followed by the elimination of H+ or condensation with CH 3OH. Additionally, the reaction of 4 with 3-penten-1-ol gave [{Ru-(P(OCH3)3)2}2{μ-SS(CH 2C=CHCH2OH)}(μ-Cl)2{μ-m-C 6H4(CH2CN)2}](CF3SO 3) (11) via the elimination of H+ and [{Ru(P(OCH 3)3)2}2(μ-SCH2CH= CHCH2S)(μ-Cl)2{μ-m-C6H 4(CH2CN)2}](CF3SO3) 2 (12) via the intramolecular elimination of a H2O molecule. 12 was exclusively obtained from the reaction of 4 with 4-bromo-1-butene.

UR - http://www.scopus.com/inward/record.url?scp=34248399260&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34248399260&partnerID=8YFLogxK

U2 - 10.1021/ic062460k

DO - 10.1021/ic062460k

M3 - Article

AN - SCOPUS:34248399260

SN - 0020-1669

VL - 46

SP - 3726

EP - 3735

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 9

ER -

C-H cleavage and double alkyl additions to the disulfido ligand in dicyanido-bridged Ru₂S₂ complexes

Abstract

Access to Document

Other files and links

Fingerprint

Cite this