Novel Method for the Preparation of Metal Cyclopropenyl Complexes from Vinylidene Complexes with an Electron-Withdrawing Substituent

Ting, Pei-Chen; Lin, Ying‐Chih; Cheng, Ming‐Chu; Yu, Wei

doi:10.1021/om00018a005

Cited by 23 publications

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“…Thus an intramolecular cycloaddition leading to the formation of the cyclopropenyl complex may be effected by a base. We have reported our preliminary results on one specific compound in a recent communication …”

Section: Introductionmentioning

confidence: 99%

Cyclopropenation and Related Reactions of Ruthenium Vinylidene Complexes

et al. 1996

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Facile deprotonation of a number of cationic ruthenium vinylidene complexes, followed by cyclopropenation, is accomplished in acetone. The deprotonation of [Ru]dCd(Ph)CH 2 R + , ([Ru] ) (η 5 -C 5 H 5 )(PPh 3 ) 2 Ru) by n-Bu 4 -NOH induces a novel cyclization reaction and yields the neutral cyclopropenyl complexes [Ru]-CdC(Ph)CHR (3b, R ) CN; 3c, R ) Ph; 3d, R ) CHdCH 2 ; 3e, R ) CHdCMe 2 ). Complex [Ru]-CdC(C 6 H 9 )CHCN + (3k) is similarly prepared. Protonation of 3b-3e regenerates the corresponding vinylidene complexes. Deprotonation of [Ru]dCdC(Ph)CH 2 COOMe + (2h) by n-Bu 4 NOH induces a different type of cyclization and yields the neutral furan complex [Ru]-CdC(Ph)CHdC(O)OMe (4h). The cyclopropenyl complex containing a methoxy substituent cannot be prepared from [Ru]dCdC(Ph)CH 2 OCH 3 + (2i), but Fof n-Bu 4 NF attacks the CR of 2i to produce the unstable vinyl complex [Ru]C(F)dC(Ph)CH 2 OCH 3 (5). Complex [Ru]-CdC(Ph)C(CN)OCH 3 (9b) was indirectly prepared from the addition of TCNQ to 3b, giving [Ru]dCdC(Ph)CH(CN)TCNQ (6b) followed by methanolysis. Unlike 3, complex 9b is not converted to vinylidene complex, instead, removal of the methoxy substituent by acid gives theis similarly prepared from 4h via a TCNQ complex 6h followed by a methoxy-substituted complex 9h. In the presence of allyl iodide, opening of the three-membered ring of 3b, followed by a subsequent oxidative coupling reaction, gives a dimeric dicationic product {[Ru]dCdC(Ph)-CHCN} 2 2+ (11). Proton abstraction of 11 by n-Bu 4 -NF gives the biscyclopropenyl complex {[Ru]-CdC(Ph)CCN} 2 (12). Molecular structures of complexes 3b, 3f, 4h, 6b, 9b, and 11 have been confirmed by X-ray diffraction analysis.

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Section: Introductionmentioning

confidence: 99%

Cyclopropenation and Related Reactions of Ruthenium Vinylidene Complexes

et al. 1996

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“…The synthesis of a number of ruthenium cyclopropenyl complexes by deprotonation of readily accessible ruthenium vinylidene complexes containing a CH 2 R group bound to Cβ has been reported [ 49 , 50 , 51 , 52 , 53 ]. A cyclopropenylruthenium complex containing pentamethylcyclopentadiethyl (Cp*) and dppp ligands was synthesized as well [ 50 ].…”

Section: Resultsmentioning

confidence: 99%

Reactivity of Ruthenium Vinylidene Complexes Containing Indenyl/dppe Ligands and Unsaturated Bonds at Cd with Trimethylsilyl Azide

Sung

Her

et al. 2012

Molecules

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This study presents a new reaction of cationic vinylidene complexes with Me3SiN3 (TMSN3), which yields N-coordinated nitrile complexes 3. Treatment of a ruthenium acetylide precursor containing indenyl and dppe ligands with a series of organic halides produced the corresponding vinylidene complexes 2 in good yield. Further reaction of 2 with TMSN3 at room temperature produced N-coordinated ruthenium nitrile complexes 3. Unlike the reaction of cyclopropenylruthenium complexes with TMSN3, which yielded different products depending on the substituent at Cγ, the vinylidene complexes containing unsaturated bonds at Cδ yielded similar N-coordinated nitrile complexes. This transformation did not seemingly occur in the reaction of ruthenium vinylidene complexes containing Cp and PPh3 ligands with TMSN3. Deprotonation of these vinylidene complexes yielded cyclopropenyl or thermodynamic furylruthenium complexes, depending on the substitute at Cγ. Subsequent reactions of the cyclopropenyl or furylruthenium complexes with TMSN3 afforded different products.

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“…The electron-withdrawing CN substituent in the vinylidene ligand of 1 (Scheme 1) not only imposes high acidity to the neighboring methylene group thus giving rise to high yield of 2; it also stabilizes the cyclopropenyl ligand after deprotonation [19]. Reactions of this complex are summarized in Scheme 1.…”

Section: Ruthenium Complex With a Cn Group On The Cyclopropenyl Ligandmentioning

confidence: 99%

Cyclopropenation of organometallic vinylidene complexes

Lin

2001

Journal of Organometallic Chemistry

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Novel Method for the Preparation of Metal Cyclopropenyl Complexes from Vinylidene Complexes with an Electron-Withdrawing Substituent

Cited by 23 publications

References 0 publications

Cyclopropenation and Related Reactions of Ruthenium Vinylidene Complexes

Cyclopropenation and Related Reactions of Ruthenium Vinylidene Complexes

Reactivity of Ruthenium Vinylidene Complexes Containing Indenyl/dppe Ligands and Unsaturated Bonds at Cd with Trimethylsilyl Azide

Cyclopropenation of organometallic vinylidene complexes

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