A Series of Vinylidene‐, Vinyl‐, Carbene‐ and Carbyneruthenium(<scp>II</scp>) Complexes with [Ru(PCy3)2] and [Ru(PiPr3)2] as Molecular Building Blocks

Jung, Stefan; Ilg, Kerstin; Brandt, Carsten D.; Wolf, Justin; Werner, Helmut

doi:10.1002/ejic.200300496

Cited by 53 publications

(14 citation statements)

References 32 publications

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“…In addition, compounds 10 – 13 show a solvatochromic behavior arising from the association of the 16 valence‐electron ruthenium moieties with Lewis‐basic solvents or react by solvolytic cleavage of the RuCl bonds to give cationic {(RCHCH)Ru(CO)(P i Pr 3 ) 2 (solv) 2 } + (e.g., solv=acetonitrile) 5. 44 Both of these processes should be largely inhibited in {Ru( η 2 ‐O 2 CC 6 H 5 )(CO)(P i Pr 3 ) 2 } 2 ( μ ‐2,5‐(CHCH) 2 ‐ c C 4 H 2 NC 6 H 5 ) ( 10 d‐benz ) with coordinatively saturated 18 valence‐electron ruthenium moieties. The latter compound was synthesized by reacting 10 d with in situ formed potassium benzoate and concomitant displacement of the chloro ligands (Experimental Section).…”

Section: Resultsmentioning

confidence: 99%

“…In addition, compounds 10-13 showasolvatochromic behavior arising from the association of the 16 valence-electron ruthenium moietiesw ith Lewis-basic solvents or react by solvolytic cleavage of the RuÀCl bonds to give cationic {(RCH=CH)Ru(CO)(PiPr 3 ) 2 (solv) 2 } + (e.g.,s olv = acetonitrile). [5,44] Both of these processes should be largely inhibited in {Ru(h 2 -…”

Section: Introductionmentioning

confidence: 99%

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Electronically Strongly Coupled Divinylheterocyclic‐Bridged Diruthenium Complexes

Pfaff

Hildebrandt

Korb

et al. 2015

Chemistry A European J

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Complexes [{Ru(CO)Cl(PiPr3 )2 }2 (μ-2,5-(CH-CH)2 -(c) C4 H2 E] (E=NR; R=C6 H4 -4-NMe2 (10 a), C6 H4 -4-OMe (10 b), C6 H4 -4-Me (10 c), C6 H5 (10 d), C6 H4 -4-CO2 Et (10 e), C6 H4 -4-NO2 (10 f), C6 H3 -3,5-(CF3 )2 (10 g), CH3 (11); E=O (12), S (13)) are discussed. The solid state structures of four alkynes and two complexes are reported. (Spectro)electrochemical studies show a moderate influence of the nature of the heteroatom and the electron-donating or -withdrawing substituents R in 10 a-g on the electrochemical and spectroscopic properties. The CVs display two consecutive one-electron redox events with ΔE°'=350-495 mV. A linear relationship between ΔE°' and the σp Hammett constant for 10 a-f was found. IR, UV/Vis/NIR and EPR studies for 10(+) -13(+) confirm full charge delocalization over the {Ru}CH-CH-heterocycle-CH-CH{Ru} backbone, classifying them as Class III systems according to the Robin and Day classification. DFT-optimized structures of the neutral complexes agree well with the experimental ones and provide insight into the structural consequences of stepwise oxidations.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electronically Strongly Coupled Divinylheterocyclic‐Bridged Diruthenium Complexes

Pfaff

Hildebrandt

Korb

et al. 2015

Chemistry A European J

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“…Moreover, isocyanate has already been successfully employed as a ligand in ruthenium-based olefin metathesis catalysts. [25][26][27] Next, we have followed up this prediction and synthesized and tested, in olefin metathesis experiments, the new isocyanate-substituted catalyst. Finally, the key step of one of the most probable decomposition reactions of 3a is investigated by DFT calculations and the mechanistic origin of the improved robustness of the new catalyst is discussed.…”

Section: Introductionmentioning

confidence: 99%

Theory-assisted development of a robust and Z-selective olefin metathesis catalyst

et al. 2014

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DFT calculations have predicted a new, highly Z-selective ruthenium-based olefin metathesis catalyst that is considerably more robust than the recently reported (SIMes)(Cl)(RS)RuCH(o-OiPrC6H4) (3a, SIMes = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene, R = 2,4,6-triphenylbenzene) [J. Am. Chem. Soc., 2013, 135, 3331]. Replacing the chloride of 3a by an isocyanate ligand to give 5a was predicted to increase the stability of the complex considerably, at the same time moderately improving the Z-selectivity. Compound 5a is easily prepared in a two-step synthesis starting from the Hoveyda-Grubbs second-generation catalyst 3. In agreement with the calculations, the isocyanate-substituted 5a appears to be somewhat more Z-selective than the chloride analogue 3a. More importantly, 5a can be used in air, with unpurified and non-degassed substrates and solvents, and in the presence of acids. These are traits that are unprecedented among highly Z-selective olefin metathesis catalysts and also very promising with respect to applications of the new catalyst.

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“…The rich reactivity of these compounds, both in terms of transformation of the alkenyl group as well as coordination chemistry at the metal centre, makes them ideal choices for exploring new mono-, bi-and tridentate ligands. [11][12][13][14][15][16][17][18][19][20] The compounds [Ru(CR 1 =CHR 2 )Cl(CO)(PPh 3 ) 2 ] 12 and [Ru(CR 1 =CHR 2 )Cl(CO)(BTD)(PPh 3 ) 2 ] (BTD = 2,1,3benzothiadiazole -a labile ligand) 17c are the most convenient triphenylphosphine-stabilised alkenyl complexes to use as starting points for this chemistry. Although many ruthenium (and to a lesser extent osmium) dithiocarbamates are known, no example has been reported with the amine-or methoxy-terminated ligands used here.…”

Section: Ruthenium and Osmium Alkenyl Complexesmentioning

confidence: 99%

“…In addition, singlets at 2.12 and 2.14 ppm were observed for the methyl protons of the terminal NMe 2 units along with pairs of multiplets for the propylene chain in the region 1.09 to 3.19 ppm. The CS 2 nucleus of the dithiocarbamate ligand gave rise to a singlet resonance at 206.1 ppm in the 13 C NMR spectrum, while the carbons of the (CH 2 ) 3 units were observed as pairs of resonances in the region 57.1 -24.9 ppm. The methyl carbons resonated at 45.5 ppm, slightly downfield of the carbons of the tert-butyl unit.…”

Section: Ruthenium and Osmium Alkenyl Complexesmentioning

confidence: 99%

The functionalisation of ruthenium(ii) and osmium(ii) alkenyl complexes with amine- and alkoxy-terminated dithiocarbamates

et al. 2010

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The complex cis-[RuCl(2)(dppm)(2)] reacts with the amine-terminated dithiocarbamates KS(2)CN(CH(2)CH(2)NEt(2))(2) and KS(2)CN(CH(2)CH(2)CH(2)NMe(2))(2) to form the compounds [Ru{S(2)CN(CH(2)CH(2)NEt(2))(2)}(dppm)(2)](+) and [Ru{S(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)}(dppm)(2)](+), respectively. The methoxy-terminated dithiocarbamate compound [Ru{S(2)CN(CH(2)CH(2)OMe)(2)}(dppm)(2)](+) was also prepared from the same precursor using KS(2)CN(CH(2)CH(2)OMe)(2). The alkenyl complexes [RuRCl(CO)(BTD)(PPh(3))(2)] (R = CH=CHBu(t), CH=CHC(6)H(4)Me-4, CH=CHCPh(2)OH), [Ru(C(C[triple bond]CBu(t))=CHBu(t))Cl(CO)(PPh(3))(2)] and [Os(CH=CHC(6)H(4)Me-4)Cl(CO)(BTD)(PPh(3))(2)] also react cleanly with KS(2)CN(CH(2)CH(2)CH(2)NMe(2))(2) and KS(2)CN(CH(2)CH(2)NEt(2))(2) to yield [MR{S(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)}(CO)(PPh(3))(2)] and [MR{S(2)CN(CH(2)CH(2)NEt(2))(2)}(CO)(PPh(3))(2)], respectively. In a similar fashion, the compounds [RuR{S(2)CN(CH(2)CH(2)OMe(2))(2)}(CO)(PPh(3))(2)] (R = CH=CHBu(t), CH=CHC(6)H(4)Me-4, C(C[triple bond]CBu(t))=CHBu(t)) were also prepared. Treatment of [Ru(CH=CHBu(t)){S(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)}(CO)(PPh(3))(2)] and [Ru{S(2)CN(CH(2)CH(2)NEt(2))(2)}(dppm)(2)](+) with trifluoroacetic acid affords the ammonium complexes [Ru(CH=CHBu(t)){S(2)CN(CH(2)CH(2)CH(2)NHMe(2))(2)}(CO)(PPh(3))(2)](2+) and [Ru{S(2)CN(CH(2)CH(2)NHEt(2))(2)}(dppm)(2)](2+), while the same reagent generates the tricationic vinylcarbene complex [Ru(=CHCH=CPh(2)){S(2)CN(CH(2)CH(2)CH(2)NHMe(2))(2)}(CO)(PPh(3))(2)](3+) through loss of water from [Ru(CH=CHCPh(2)OH){S(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)}(CO)(PPh(3))(2)]. The structures of [Ru{S(2)CN(CH(2)CH(2)OMe)(2)}(dppm)(2)]PF(6) and [Ru(CH=CHC(6)H(4)Me-4){S(2)CN(CH(2)CH(2)OMe)(2)}(CO)(PPh(3))(2)] were determined crystallographically.

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A Series of Vinylidene‐, Vinyl‐, Carbene‐ and Carbyneruthenium(II) Complexes with [Ru(PCy₃)₂] and [Ru(PiPr₃)₂] as Molecular Building Blocks

Abstract: The hydrido (vinylidene)

Cited by 53 publications

References 32 publications

Electronically Strongly Coupled Divinylheterocyclic‐Bridged Diruthenium Complexes

Electronically Strongly Coupled Divinylheterocyclic‐Bridged Diruthenium Complexes

Theory-assisted development of a robust and Z-selective olefin metathesis catalyst

The functionalisation of ruthenium(ii) and osmium(ii) alkenyl complexes with amine- and alkoxy-terminated dithiocarbamates

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A Series of Vinylidene‐, Vinyl‐, Carbene‐ and Carbyneruthenium(II) Complexes with [Ru(PCy3)2] and [Ru(PiPr3)2] as Molecular Building Blocks

Abstract: The hydrido (vinylidene)

Cited by 53 publications

References 32 publications

Electronically Strongly Coupled Divinylheterocyclic‐Bridged Diruthenium Complexes

Electronically Strongly Coupled Divinylheterocyclic‐Bridged Diruthenium Complexes

Theory-assisted development of a robust and Z-selective olefin metathesis catalyst

The functionalisation of ruthenium(ii) and osmium(ii) alkenyl complexes with amine- and alkoxy-terminated dithiocarbamates

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A Series of Vinylidene‐, Vinyl‐, Carbene‐ and Carbyneruthenium(II) Complexes with [Ru(PCy₃)₂] and [Ru(PiPr₃)₂] as Molecular Building Blocks