Addition von Phosphanen an das Cα-Atom von allenyliden(pentacarbonyl)chrom und umlagerung in phosphan-komplexe

Fischer, Helmut; Reindl, David; Troll, Carsten; Leroux, Frédéric R.

doi:10.1016/0022-328x(94)05210-3

Cited by 28 publications

(16 citation statements)

References 22 publications

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“…Fischer has also reported that the allenylidene complex [Cr(CO) 5 {CCC(C 6 H 4 NMe 2 - p ) 2 }] adds phosphines at the C α carbon atom to give ylide complexes [Cr(CO) 5 {η 1 -C(PR 3 )CC(C 6 H 4 NMe 2 - p ) 2 }] (PR 3 = PMe 3 , PHPh 2 , PH 2 Mes). At room temperature, the complex [Cr(CO) 5 {η 1 -C(PHPh 2 )CC(C 6 H 4 NMe 2 - p ) 2 }] rearranges to [Cr(CO) 5 {PPh 2 [CHCC(C 6 H 4 NMe 2 - p ) 2 ]}] …”

Section: Resultsmentioning

confidence: 99%

Five-Coordinate Complex [RuHCl(CO)(PPrⁱ₃)₂] as a Precursor for the Preparation of New Cyclopentadienylruthenium Compounds Containing Unsaturated η¹-Carbon Ligands

et al. 1996

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The five-coordinate complex [RuHCl(CO)(PPri 3)2] (1) reacts with cyclopentadiene in methanol under reflux to give [RuH(η5-C5H5)(CO)(PPri 3)] (2) and [HPPri 3]Cl. The protonation of 2 in dichloromethane-d 2 leads to the dihydrogen complex [Ru(η5-C5H5)(η2-H2)(CO)(PPri 3)]BF4 (3) in equilibrium with traces of the dihydrido tautomer [RuH2(η5-C5H5)(CO)(PPri 3)]BF4 (4). The reaction of 2 with HBF4·Et2O in acetone affords the solvated complex [Ru(η5-C5H5)(CO){η1-OC(CH3)2}(PPri 3)]BF4 (5), which reacts with CO, dimethyl acetylenedicarboxylate, and NaCl to give [Ru(η5-C5H5)(CO)2(PPri 3)]BF4 (6), [Ru(η5-C5H5){η2-C2(CO2CH3)2}(CO)(PPri 3)]BF4 (7), and [Ru(η5-C5H5)Cl(CO)(PPri 3)] (8), respectively. Complex 5 also reacts with alkyn-1-ols. The reaction with 1,1-diphenyl-2-propyn-1-ol leads to the allenylidene complex [Ru(η5-C5H5)(CCCPh2)(CO)(PPri 3)]BF4 (9), which affords [Ru(η5-C5H5){C(OH)CHCPh2}(CO)(PPri 3)]BF4 (10) by reaction with water. 10 is converted into the acyl derivative [Ru(η5-C5H5){C(O)CHCPh2}(CO)(PPri 3)] (11), when a CH2Cl2 solution of 10 is passed through an Al2O3 column. The structure of 11 was determined by an X-ray investigation. The reaction of 5 with 2-propyn-1-ol leads to the α,β-unsaturated hydroxycarbene complex [Ru(η5-C5H5){C(OH)CHCH2}(CO)(PPri 3)]BF4 (12). Similarly to 10, 12 is converted into [Ru(η5-C5H5){C(O)CHCH2}(CO)(PPri 3)] (13), when the solutions of 12 are passed through an Al2O3 column. Treatment of 5 with 1-ethynyl-1-cyclohexanol leads to a mixture of organometallic compounds including [Ru(η5-C5H5){C(OH)CHC(CH2)4CH2}(CO)(PPri 3)]BF4 (14). Chromatography of the mixture affords [Ru(η5-C5H5){C(O)CHC(CH2)4CH2}(CO)(PPri 3)] (15) and [Ru(η5-C5H5){C⋮CCCH(CH2)3CH2}(CO)(PPri 3)] (16). 9 reacts with alcohols and thiols to give [Ru(η5-C5H5){C(ER)CHCPh2}(CO)(PPri 3)]BF4 (ER = OMe (17), OEt (18), SPrn (21)), which by treatment with NaOMe afford [Ru(η5-C5H5){C(ER)CCPh2}(CO)(PPri 3)] (ER = OMe (19), OEt (20), SPrn (22)). Similarly, the reaction of 9 with benzophenone imine leads to [Ru(η5-C5H5){C(CHCPh2)NCPh2}(CO)(PPri 3)]BF4 (23), which by reaction with NaOMe gives [Ru(η5-C5H5){C(NCPh2)CCPh2}(CO)(PPri 3)] (24). The structure of 23 was also determined by an X-ray investigation. The CN bond lengths are 1.283(9) and 1.252(9) Å, while the C−N−C angle is 149.9(6)°.

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Section: Resultsmentioning

confidence: 99%

Five-Coordinate Complex [RuHCl(CO)(PPrⁱ₃)₂] as a Precursor for the Preparation of New Cyclopentadienylruthenium Compounds Containing Unsaturated η¹-Carbon Ligands

et al. 1996

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“…Fischer has reported that the allenylidene complex Cr(CO) 5 {CCC(C 6 H 4 NMe 2 - p ) 2 } adds phosphines at the α-carbon atom to give ylide complexes Cr(CO) 5 {C(PR 3 )CC(C 6 H 4 NMe 2 - p ) 2 } (PR 3 = PMe 3 , PHPh 2 , PH 2 Mes). At room temperature, the complex Cr(CO) 5 {C(PHPh 2 )CC(C 6 H 4 NMe 2 - p ) 2 } rearranges to Cr(CO) 5 {PPh 2 [CHCC(C 6 H 4 NMe 2 - p ) 2 ]} …”

Section: Resultsmentioning

confidence: 99%

Addition of Carbon Nucleophiles to the Allenylidene Ligand of [Ru(η⁵-C₅H₅)(CCCPh₂)(CO)(PⁱPr₃)]BF₄: Synthesis of New Organic Ligands by Formal C−C Coupling between Mutually Inert Fragments

et al. 1997

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EHT-MO Calculations on the model cation [Ru(η5-C5H5)(CCCH2)(CO)(PH3)]+ (1a) suggest that 23% and 31% of the LUMO and 26% of the HOMO of [Ru(η5-C5H5)(CCCPh2)(CO)(PiPr3)]BF4 (1) are located on Cα, Cγ, and Cβ of the allenylidene ligand, respectively. On the basis of these results, we report a new synthetic strategy for the preparation of compounds resulting from the formal addition of phenylacetylene, acetone, and methane to the allenylidene of 1. Treatment of 1 with LiC⋮CPh leads to the allenyl complex Ru(η5-C5H5){C(C⋮CPh)CCPh2}(CO)(PiPr3) (2) and the alkynyl derivative Ru(η5-C5H5){C⋮C−C(Ph)2C⋮CPh}(CO)(PiPr3) (3). The reaction of 2 with HBF4 affords the substituted carbene compound [Ru(η5-C5H5){C(C⋮CPh)CHCPh2}(CO)(PiPr3)]BF4 (4), which is a result from the formal addition of phenylacetylene to the Cα−Cβ double bond of the allenylidene of 1. The molecular structure of 4 has been determined by X-ray crystallography. The geometry around the ruthenium center is close to octahedral with the cyclopentadienyl ligand occupying three sites of a face. The RuC bond length is 2.004(5) Å. In the presence of KOH, complex 1 reacts with acetone to give Ru(η5-C5H5){C⋮C−C(Ph)2CH2C(O)CH3}(CO)(PiPr3) (5). The reaction of 5 with HBF4 leads to the unsaturated cyclic carbene Complex 5 also reacts with 2 equiv of CF3CO2D to and CF3CO2H, and the reaction of Ru(η5-C5H5){C⋮C−C(Ph)2CD2C(O)CD3}(CO)(PiPr3) (5- d 5 ) with 2 equiv of HBF4 and DBF4. On the basis of these isotope labeling experiments, the mechanism for the addition of acetone to the allenylidene ligand of 1 is discussed. Complex 1 also reacts with Na(acac) and CH3Li. The reaction with Na(acac) leads to Ru(η5-C5H5){C⋮C−C(Ph)2CH[C(O)CH3]2}(CO)(PiPr3) (7), while the treatment of 1 with CH3Li gives a mixture of Ru(η5-C5H5){C(CH3)CCPh2}(CO)(PiPr3) (8) and Ru(η5-C5H5){C⋮C−C(Ph)2CH3}(CO)(PiPr3) (9). Complex 9 reacts with HBF4 to afford [Ru(η5-C5H5){CCHC(Ph)2CH3}(CO)(PiPr3)]BF4 (10), which is a result of the formal addition of a C−H bond of methane to the Cβ−Cγ double bond of the allenylidene of 1.

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“…When C g adducts are initially formed, they slowly isomerize to give the C a phosphane adducts. When secondary phosphanes are employed in the reactions with diarylallenylidene complexes, the C a adducts rearrange by insertion of the phosphane into the metalÁ/C a bond affording various types of phosphane complexes [26].…”

Section: Reactionsmentioning

confidence: 99%

A new method for the preparation of N-stabilized allenylidene complexes of chromium and tungsten

Fischer¹,

Szesni²,

Roth³

et al. 2003

Journal of Organometallic Chemistry

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Displacement of tetrahydrofuran in [(CO) 5 M(THF)] (M 0/Cr, W) by the anion [C Å/C Ã/C(Ä/X)Y] ((X 0/O; NR; Y 0/NR ? 2 , Ph) followed by alkylation of the resulting metalate with [R ƒ 3 O]BF 4 (R ƒ0/Me, Et) offers a convenient and versatile route to p-donorsubstituted allenylidene complexes, [(CO) 5 M Ä/C Ä/C Ä/C(XR ƒ)Y]. Allenylidene complexes in which the terminal carbon atom of the allenylidene ligand constitutes part of a heterocycle are likewise accessible by this reaction sequence. Reaction of [(CO) 5 M(THF)] with Li[C Å/C Ã/C(Ä/NMe)Ph] (and subsequent protonation of the metalate afford [(CO) 5 M Ä/C Ä/C Ä/C(NMeH)Ph] in high yield. As indicated by the spectroscopic data of the compounds and the X-ray analyses of three representative examples, these allenylidene complexes are best described as hybrids of allenylidene and zwitterionic alkynyl complexes with delocalisation of the electron pair at nitrogen towards the metal center. Dimethylamine reacts with the amino(phenyl)allenylidene complex [(CO) 5 Cr Ä/C Ä/C Ä/ C(NMe 2)Ph] (7a) by addition of the amine across the C a Ä/C b bond to give selectively the E-alkenyl(amino)carbene complex [(CO) 5 Cr Ä/C(NMe 2) Ã/CH Ä/C(NMe 2)Ph] (12). In contrast, the reaction of dimethylamine with the amino(methoxy)allenylidene complex [(CO) 5 Cr Ä/C Ä/C Ä/C(NMe 2)OMe] (1a) proceeds by addition of the amine to the C g atom and subsequent elimination of methanol to give the substitution product [(CO) 5 Cr Ä/C Ä/C Ä/C(NMe 2) 2 ] (13). Triphenylphosphane neither adds to the C a nor the C g atom of 7a but upon irradiation displaces a CO ligand to form a cis-allenylidene(tetracarbonyl)phosphane complex 15.

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Addition von Phosphanen an das Cα-Atom von allenyliden(pentacarbonyl)chrom und umlagerung in phosphan-komplexe

Cited by 28 publications

References 22 publications

Five-Coordinate Complex [RuHCl(CO)(PPrⁱ₃)₂] as a Precursor for the Preparation of New Cyclopentadienylruthenium Compounds Containing Unsaturated η¹-Carbon Ligands

Five-Coordinate Complex [RuHCl(CO)(PPrⁱ₃)₂] as a Precursor for the Preparation of New Cyclopentadienylruthenium Compounds Containing Unsaturated η¹-Carbon Ligands

Addition of Carbon Nucleophiles to the Allenylidene Ligand of [Ru(η⁵-C₅H₅)(CCCPh₂)(CO)(PⁱPr₃)]BF₄: Synthesis of New Organic Ligands by Formal C−C Coupling between Mutually Inert Fragments

A new method for the preparation of N-stabilized allenylidene complexes of chromium and tungsten

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Addition von Phosphanen an das Cα-Atom von allenyliden(pentacarbonyl)chrom und umlagerung in phosphan-komplexe

Cited by 28 publications

References 22 publications

Five-Coordinate Complex [RuHCl(CO)(PPri3)2] as a Precursor for the Preparation of New Cyclopentadienylruthenium Compounds Containing Unsaturated η1-Carbon Ligands

Five-Coordinate Complex [RuHCl(CO)(PPri3)2] as a Precursor for the Preparation of New Cyclopentadienylruthenium Compounds Containing Unsaturated η1-Carbon Ligands

Addition of Carbon Nucleophiles to the Allenylidene Ligand of [Ru(η5-C5H5)(CCCPh2)(CO)(PiPr3)]BF4: Synthesis of New Organic Ligands by Formal C−C Coupling between Mutually Inert Fragments

A new method for the preparation of N-stabilized allenylidene complexes of chromium and tungsten

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Five-Coordinate Complex [RuHCl(CO)(PPrⁱ₃)₂] as a Precursor for the Preparation of New Cyclopentadienylruthenium Compounds Containing Unsaturated η¹-Carbon Ligands

Five-Coordinate Complex [RuHCl(CO)(PPrⁱ₃)₂] as a Precursor for the Preparation of New Cyclopentadienylruthenium Compounds Containing Unsaturated η¹-Carbon Ligands

Addition of Carbon Nucleophiles to the Allenylidene Ligand of [Ru(η⁵-C₅H₅)(CCCPh₂)(CO)(PⁱPr₃)]BF₄: Synthesis of New Organic Ligands by Formal C−C Coupling between Mutually Inert Fragments