Basische Metalle, LIV. Ringverbrückte Rhodium‐Zweikernkomplexe mit (C
 5
 H
 4
 )
 2
 CH
 2
 ‐ und (C
 5
 H
 4
 )
 2
 SiMe
 2
 ‐Dianionen als Brückenliganden. Kristall‐ und Molekülstruktur von [(C
 5
 H

Werner, Helmut; Scholz, Hans Jürgen; Zolk, R.

doi:10.1002/cber.19851181123

Cited by 32 publications

(4 citation statements)

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“…rahedral angle. In the less strained binuclear rhodium complex However, both of the binuclear species 5 and 9 can be pro- (16) and in the analogous tonated by HBF4.0Et, to form cationic hydridometal deriva-…”

Section: Resultsmentioning

confidence: 99%

“…The procedure was analogous to that described for 10, using 9 (84 mg, 0.12 mmol) and a 54% solution of HBF, (16 A solution of 15 (173 mg, 0.37 mmol) in 15 mL of hexane was treated, at -78"C, dropwise with a 1.6 M solution (0.23 mL, 0.37 mmol) of nBuLi in hexane. After the reaction mixture was warmed to room temperature, it was stirred for 1 h, and then the solvent was removed.…”

Section: Ch=chtbu)])bf 11mentioning

confidence: 99%

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Novel binuclear doubly vinyl-bridged iridium complexes formed by olefinic C—H activation

Werner¹,

Wolf²,

Nessel³

et al. 1995

Can. J. Chem.

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Section: Resultsmentioning

confidence: 99%

Section: Ch=chtbu)])bf 11mentioning

confidence: 99%

Novel binuclear doubly vinyl-bridged iridium complexes formed by olefinic C—H activation

Werner¹,

Wolf²,

Nessel³

et al. 1995

Can. J. Chem.

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“…[Rh(C 2 H 4 ) 2 (l-Cl)] 2 was first synthesised according to the method of Cramer. 32 [CH 2 (C 5 H 4 ) 2 ][Rh(C 2 H 4 ) 2 ] 2 was synthesised using a modification of the method described by Werner et al 33 [Rh(C 2 H 4 ) 2 (l-Cl)] 2 (0.5 g) was added to a cooled (−78 • C) Schlenk tube containing CH 2 [(C 5 H 4 )Tl] 2 (0.99 g). THF (30 ml) was slowly transferred into the Schlenk tube with continual stirring and the solvent removed after 30 minutes.…”

Section: Synthesis Of [Ch 2 (C 5 H 4 ) 2 ][Rh(c 2 H 4 ) 2 ] 2mentioning

confidence: 99%

“…Reduction with Na and reaction with MeI generated the M-M bond containing species [CH 2 (g 5 -C 5 H 4 ) 2 ][Co(Me)(l-CO)] 2 . In 1985, Werner et al 24 synthesised [CH 2 (g 5 -C 5 H 4 ) 2 ][Rh(C 2 H 4 ) 2 ] 2 (1) and several related dinuclear rhodium complexes, and reported on a number of their thermal reactions. 25 Here we describe how the dinuclear rhodium complex [CH 2 (g 5 -C 5 H 4 ) 2 ][Rh(C 2 H 4 ) 2 ] 2 1 reacts with dmso, CH 2 =CHSiMe 3 , Et 3 SiH, Et 2 SiH 2 and Me 3 SiH under photochemical conditions.…”

Section: Introductionmentioning

confidence: 99%

Photochemical reactions of [CH₂(η⁵-C₅H₄)₂][Rh(C₂H₄)₂]₂with silanes: evidence for Si–C and C–H activation pathways

Cunningham

Duckett

2005

Dalton Trans.

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Photochemical reaction of [CH2(eta5-C5H4)2][Rh(C2H4)2]2 1 with dmso led to the stepwise formation of [CH2(eta5-C5H4)2][Rh(C2H4)2][Rh(C2H4)(dmso)] 2a and [CH2(eta5-C5H4)2][Rh(C2H4)(dmso)]2 2b. Photolysis of 1 with vinyltrimethylsilane ultimately yields three isomeric products of [CH2(eta5-C5H4)2][Rh(CH2=CHSiMe3)2]2, 3a, 3b and 3c which are differentiated by the relative orientations of the vinylsilane. When this reaction is undertaken in d6-benzene, H/D exchange between the solvent and the alpha-proton of the vinylsilane is revealed. In addition evidence for two isomers of the solvent complex [CH2(eta5-C5H4)2][Rh(C2H4)2][Rh(C2H4)(eta2-toluene)] was obtained in these and related experiments when the photolysis was completed at low temperature without substrate, although no evidence for H/D exchange was observed. Photolysis of 1 with Et3SiH yielded the sequential substitution products [CH2(eta5-C5H4)2][Rh(C2H4)2][Rh(C2H4)(SiEt3)H] 4a, [CH2(eta5-C5H4)2][Rh(C2H4)(SiEt3)H]2 4b, [CH2(eta5-C5H4)2][Rh(C2H4)(SiEt3)H][Rh(SiEt3)2(H)2] 4c and [CH2(eta5-C5H4)2][Rh(SiEt3)2(H)2]2 4d; deuteration of the alpha-ring proton sites, and all the silyl protons, of 4d was demonstrated in d6-benzene. This reaction is further complicated by the formation of two Si-C bond activation products, [CH2(eta5-C5H4)2][RhH(mu-SiEt2)]2 5 and [CH2(eta5-C5H4)2][(RhEt)(RhH)(mu-SiEt2)2] 6. Complex 5 was also produced when 1 was photolysed with Et2SiH2. When the photochemical reactions with Et3SiH were repeated at low temperatures, two isomers of the unstable C-H activation products, the vinyl hydrides [CH2(eta5-C5H4)2][{Rh(SiEt3)H}{Rh(SiEt3)}(mu-eta1,eta2-CH=CH2)] 7a and 7b, were obtained. Thermally, 4c was shown to form the ring substituted silyl migration products [(eta5-C5H4)CH2(C5H3SiEt3)][Rh(SiEt3)2(H)2]2 8 while 4b formed [CH2(C5H3SiEt3)2][Rh(SiEt3)2(H)2]2 (9a and 9b) upon reaction with excess silane. The corresponding photochemical reaction with Me3SiH yielded the expected products [CH2(eta5-C5H4)2][Rh(C2H4)2][Rh(C2H4)(SiMe3)H] 10a, [CH2(eta5-C5H4)2][Rh(C2H4)(SiMe3)H]2 10b, [CH2(eta5-C5H4)2][Rh(C2H4)(SiMe3)H][Rh(SiMe3)2(H)2] 10c and [CH2(eta5-C5H4)2][Rh(SiMe3)2(H)2]2 10d. However, three Si-C bond activation products, [CH2(eta5-C5H4)2][(RhMe)(RhH)(mu-SiMe2)2] 11, [CH2(eta5-C5H4)2][(Rh{SiMe3})(RhMe)(mu-SiMe2)2] 12 and [CH2(eta5-C5H4)2][(Rh{SiMe3})(RhH)(mu-SiMe2)2] 13 were also obtained in these reactions.

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Erste heterodinucleare Komplexe mit Bis(cyclopentadienyl)methan‐Brücken

et al. 1989

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tion der Kristallstruktur in 5 zeigt. C-4a des Isoalloxazins und die S-Atome der Disulfidbriicke liegen linear iibereinander, und die energetisch fast entarteten Grenzorbitale (HO-MO~,,,,e~-LUMO~,-,,,,~ cys63)) ergeben eine kraftige kovalente Wechselwirkung zwischen C-4a und dem Schwefelatom von Cys63.5 unterstreicht zudem die giinstige Ausrichtung der Orbitale fur einen Riickseitenangriff von C-4a auf die Disulfidbindung. Der Ablauf 1aDt sich als nucleophile Spaltung der SS-Briicke unter Bildung einer kovalenten Bindung zwischen C-4a des Isoalloxazins und dem S-Atom von C VCH kr/agsgese/lTchafr mbH, 0-6940 Wemheim, 19x9 0044-8249~89j0808-1058 3 02.50j0

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Basische Metalle, LIV. Ringverbrückte Rhodium‐Zweikernkomplexe mit (C ₅ H ₄ ) ₂ CH ₂ ‐ und (C ₅ H ₄ ) ₂ SiMe ₂ ‐Dianionen als Brückenliganden. Kristall‐ und Molekülstruktur von [(C ₅ H

Cited by 32 publications

References 24 publications

Novel binuclear doubly vinyl-bridged iridium complexes formed by olefinic C—H activation

Novel binuclear doubly vinyl-bridged iridium complexes formed by olefinic C—H activation

Photochemical reactions of [CH₂(η⁵-C₅H₄)₂][Rh(C₂H₄)₂]₂with silanes: evidence for Si–C and C–H activation pathways

Erste heterodinucleare Komplexe mit Bis(cyclopentadienyl)methan‐Brücken

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Basische Metalle, LIV. Ringverbrückte Rhodium‐Zweikernkomplexe mit (C 5 H 4 ) 2 CH 2 ‐ und (C 5 H 4 ) 2 SiMe 2 ‐Dianionen als Brückenliganden. Kristall‐ und Molekülstruktur von [(C 5 H

Cited by 32 publications

References 24 publications

Novel binuclear doubly vinyl-bridged iridium complexes formed by olefinic C—H activation

Novel binuclear doubly vinyl-bridged iridium complexes formed by olefinic C—H activation

Photochemical reactions of [CH2(η5-C5H4)2][Rh(C2H4)2]2with silanes: evidence for Si–C and C–H activation pathways

Erste heterodinucleare Komplexe mit Bis(cyclopentadienyl)methan‐Brücken

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Basische Metalle, LIV. Ringverbrückte Rhodium‐Zweikernkomplexe mit (C ₅ H ₄ ) ₂ CH ₂ ‐ und (C ₅ H ₄ ) ₂ SiMe ₂ ‐Dianionen als Brückenliganden. Kristall‐ und Molekülstruktur von [(C ₅ H

Photochemical reactions of [CH₂(η⁵-C₅H₄)₂][Rh(C₂H₄)₂]₂with silanes: evidence for Si–C and C–H activation pathways