Vanadocene, Bis(η
            <sup>5</sup>
            ‐Cyclopentadienyl) Vanadium

Floriani, Carlo; Mange, Vladimir; Barefield, E. Kent; Carris, Michael W.

doi:10.1002/9780470132593.ch67

Cited by 18 publications

(1 citation statement)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…UV‐Vis spectra were recorded on an Analytik Jena SPECORD 200 with 10.00 mm quartz glass cuvettes equipped with PTFE plugs. CpVC 6 H 6 ( 1 ) was synthesized in multiple steps (VCl 3 (thf) 3 , [V 2 Cl 3 (thf) 6 ] 2 [ZnCl 6 ], NaCp, Cp 2 V) starting from VCl 3 using scaled literature procedures [30c,d,47] . Visualizations of quantum chemical calculation results were created with VESTA 3 [48] and the contour plot was created with Multiwfn [49] .…”

Section: Methodsmentioning

confidence: 99%

Vanadium Pentafulvene Complexes: Synthon for Unprecedented Vanadocene^IIIDerivatives

Graaff

Schwitalla

Thye

et al. 2023

Chemistry A European J

View full text Add to dashboard Cite

The benzene ligand at CpV(η 6 À C 6 H 6 ) (1) is exchanged for pentafulvenes. Using sterically demanding pentafulvenes gives a clean exchange reaction, yielding vanadium pentafulvene (2 a and 2 b) and benzofulvene complexes (3 a and 3 b). The molecular structures of the target compounds suggest a π-η 5 :σ-η 1 coordination mode with a vanadium III center. With the sterically low demanding 6,6-dimethylpentafulvene, a CÀ H activation at the leaving ligand is observed, yielding the ring-substituted vanadocene II 4. The reactivity of the pentafulvene complexes was investigated. A series of unprecedented vanadocene III compounds were synthesized: Under mild conditions, EÀ H splitting of 4tert-butylphenol, diphenylamine, and 2,6-diisopropylaniline yield well characterized examples of rare vanadocene III phenolate and amide complexes. Insertion reactions into the VÀ C exo bond of the pentafulvene complexes by multiple bond containing substrates were found for acetone, 4-chlorobenzonitril and N,N'-dicyclohexylcarbodiimide.

show abstract

Section: Methodsmentioning

confidence: 99%

Vanadium Pentafulvene Complexes: Synthon for Unprecedented Vanadocene^IIIDerivatives

Graaff

Schwitalla

Thye

et al. 2023

Chemistry A European J

View full text Add to dashboard Cite

show abstract

[Cp2V] Migration along an Octatetrayne Chain: From the Monometallic Complex [Cp2V(3-4η-tBuC≡C−C2−C≡CC≡CtBu)] to the Dimetallic Complex [(Cp2V)2(1-2η:7-8η-tBuC2−C≡CC≡C−C2tBu)]

et al. 2000

View full text Add to dashboard Cite

The oxidative addition of one equivalent of [Cp2V] (4) to the tetrayne ligand tBuC triple bond CC triple bond CC triple bond CC triple bond CtBu (5) gives the monometallic complex [Cp2V(3-4eta-tBuC triple bond C-C2-C triple bond CC triple bond CtBu)] (7). Compound 7 reacts further with a second equivalent of [Cp2V] to give the dimetallic complex [(Cp2V)2(1-2eta:7-8eta-tBuC2-C triple bond CC triple bond C-C2tBu)] (8), which involves a shift of the first coordinated [Cp2V] unit from the internal C3-C4 to the external C1-C2 positions on the alkynyl ligand. Compound 8 is also directly obtained by the addition of two equivalents of [Cp2V] to 5. Reversibly, reaction of 8 with 5 leads to 7. This exchange reaction between 7 and 8 by adding successively 5 and 4 has been monitored by EPR spectroscopy. By contrast, the oxidative addition of one or two equivalents of [Cp2V] to the tetrayne ligand PhC triple bond CC triple bond CC triple bond CC triple bond CPh (6) gives the homodimetallic complex [(Cp2V)2(1-2eta:7-8eta-PhC2-CC triple bond CC triple bond C-C2-Ph)] (9). Both monometallic and dimetallic complexes 7, 8, and 9 have been characterized by X-ray diffraction. Magnetic moment measurements for 8 and 9 from 300 to 4 K indicated a weak antiferromagnetic J exchange coupling of -12.5 and -4.1 cm(-1), respectively.

show abstract

Electro‐ and Magnetocommunication in [5,5]Ditrovacenyls, [(η⁷‐C₇H₇)V(η⁵‐C₅H₄‐X‐η⁵‐C₅H₄)V(η⁷‐C₇H₇)], Mediated by the Spacers X=(Z)CHCH, (E)CHCH, >CCH₂, CH₂CH₂, and CH₂

Elschenbroich

Plackmeyer

Nowotny

et al. 2005

Chemistry A European J

View full text Add to dashboard Cite

Five new paramagnetic dinuclear complexes containing [5]trovacenyl groups, (eta7-C7H7)V(eta5-C5H4-), have been prepared and characterized, including by single-crystal X-ray diffraction. As intervening spacers, ethenediyl units in the geminal and vicinal (Z)- and (E)-bridging modes as well as methanediyl and ethanediyl units have been included with the aim of studying their propensity to transmit electric and magnetic information. It is found that redox splitting of consecutive electron-transfer steps is resolved for reduction (0-->1- -->2-) only, unsaturation of the C2 bridge not being requisite, since the -CH2CH2- spacer also gives rise to a small redox splitting. Magnetic communication is quantified in terms of the exchange coupling constant J, accessible from the EPR hyperfine pattern in solution and from magnetic susceptometry in the solid state. The results obtained from these methods generally differ; this fact is not surprising in view of conformational differences in the respective states of aggregation. It is concluded that orientation-dependent mechanisms of spin-spin interactions (pi-orbital overlap, hyperconjugation) contribute extensively although, as implied by sizeable J values for -CH2- and -C2H4- linked di[5]trovacenyl groups, coupling mediated by the sigma-orbital chain must also be considered.

show abstract

Vanadocene, Bis(η ⁵ ‐Cyclopentadienyl) Vanadium

Cited by 18 publications

References 6 publications

Vanadium Pentafulvene Complexes: Synthon for Unprecedented Vanadocene^IIIDerivatives

Vanadium Pentafulvene Complexes: Synthon for Unprecedented Vanadocene^IIIDerivatives

[Cp2V] Migration along an Octatetrayne Chain: From the Monometallic Complex [Cp2V(3-4η-tBuC≡C−C2−C≡CC≡CtBu)] to the Dimetallic Complex [(Cp2V)2(1-2η:7-8η-tBuC2−C≡CC≡C−C2tBu)]

Electro‐ and Magnetocommunication in [5,5]Ditrovacenyls, [(η⁷‐C₇H₇)V(η⁵‐C₅H₄‐X‐η⁵‐C₅H₄)V(η⁷‐C₇H₇)], Mediated by the Spacers X=(Z)CHCH, (E)CHCH, >CCH₂, CH₂CH₂, and CH₂

Contact Info

Product

Resources

About

Vanadocene, Bis(η 5 ‐Cyclopentadienyl) Vanadium

Cited by 18 publications

References 6 publications

Vanadium Pentafulvene Complexes: Synthon for Unprecedented VanadoceneIIIDerivatives

Vanadium Pentafulvene Complexes: Synthon for Unprecedented VanadoceneIIIDerivatives

[Cp2V] Migration along an Octatetrayne Chain: From the Monometallic Complex [Cp2V(3-4η-tBuC≡C−C2−C≡CC≡CtBu)] to the Dimetallic Complex [(Cp2V)2(1-2η:7-8η-tBuC2−C≡CC≡C−C2tBu)]

Electro‐ and Magnetocommunication in [5,5]Ditrovacenyls, [(η7‐C7H7)V(η5‐C5H4‐X‐η5‐C5H4)V(η7‐C7H7)], Mediated by the Spacers X=(Z)CHCH, (E)CHCH, >CCH2, CH2CH2, and CH2

Contact Info

Product

Resources

About

Vanadocene, Bis(η ⁵ ‐Cyclopentadienyl) Vanadium

Vanadium Pentafulvene Complexes: Synthon for Unprecedented Vanadocene^IIIDerivatives

Vanadium Pentafulvene Complexes: Synthon for Unprecedented Vanadocene^IIIDerivatives

Electro‐ and Magnetocommunication in [5,5]Ditrovacenyls, [(η⁷‐C₇H₇)V(η⁵‐C₅H₄‐X‐η⁵‐C₅H₄)V(η⁷‐C₇H₇)], Mediated by the Spacers X=(Z)CHCH, (E)CHCH, >CCH₂, CH₂CH₂, and CH₂