Insertion reactions of bis(η5-cyclopentadienyl)-dihydridotungsten with activated olefins and with acetylenes: Tungstenocene alkyl hydrides, olefin and acetylene complexes

Herberich, Gerhard E.; Barlage, W.; Linn, Klaus

doi:10.1016/0022-328x(91)86101-u

Cited by 13 publications

(4 citation statements)

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“…Bis(η 5 -cyclopentadienyl)tungsten dihydride was first synthesized in 1961, and subsequently there have been numerous reports of its uses and importance in inorganic and organometallic chemistry. − The spectroscopic investigation of (C 5 H 5 ) 2 WH 2 was initiated by Green et al in 1961 . In their initial paper detailing the synthesis of the title complex, the authors performed a high-resolution NMR study of (C 5 H 5 ) 2 WH 3 + , obtained by dissolving the dihydride in concentrated HCl.…”

Section: Introductionmentioning

confidence: 99%

Microwave Spectra and Gas-Phase Structural Parameters of Bis(η⁵-cyclopentadienyl)tungsten Dihydride

et al. 2007

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Microwave spectra for 11 isotopomers of bis(η 5 -cyclopentadienyl)tungsten dihydride ((C 5 H 5 ) 2 WH 2 ) were recorded in the 5-14 GHz region using a Flygare-Balle-type pulsed beam spectrometer. Spectra arising from four tungsten isotopomers of both the (C 5 H 5 ) 2 WH 2 and (C 5 H 5 ) 2 WHD species and three W isotopomers for the (C 5 H 5 ) 2 WD 2 complex have been measured. The ∼250 b-type transition frequencies assigned for these near-prolate asymmetric top molecules were accurately described (σ fit ) 2-4 kHz) using the rotational parameters A, B, and C and one centrifugal distortion constant, ∆ J . The small value obtained for ∆ J indicates a fairly rigid structure. From a least-squares fit using the resulting 33 rotational constants to obtain the molecular structure, we were able to determine the W-H bond length, r(W-H) ) 1.703(2) Å, the H-W-H bond angle, ∠(H-W-H) ) 78.0(12)°, the W-Cp centroid distance, r(W-Cp) ) 1.940(8) Å, the angle made by the Cp centroids with tungsten, ∠(Cp-W-Cp) ) 155(2)°, and the average C-C bond length, r(C-C) ) 1.429(8) Å. The hydrogen atom separation is r(H-H) ) 2.14(2) Å, indicating that this is clearly a "classical dihydride" rather than an "η 2 -dihydrogen" complex. The WH 2 moiety parameters determined from Kraitchman's equations (r(W-H) ) 1.682(2) Å, ∠(H-W-H) ) 78.6(2), r(H-H) ) 2.130(2) Å) agree well with the least-squares results. Furthermore, the r e parameters obtained from DFT calculations agree well with the experimental r 0 structural parameters. To our knowledge, this work marks the first microwave study of a bent-metallocene complex. The present measurements were made with a pulsed-beam Fourier transform spectrometer employing a homodynetype detection system, and this configuration is described. This homodyne system greatly simplifies the microwave circuit, with no apparent loss in sensitivity.

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Section: Introductionmentioning

confidence: 99%

Microwave Spectra and Gas-Phase Structural Parameters of Bis(η⁵-cyclopentadienyl)tungsten Dihydride

et al. 2007

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“…The structure consisted of well-separated monomeric units with no short intermolecular contacts. The overall pseudotetrahedral geometry of 1 has similar bond angles to an alkyl hydride of tungsten, and the B−H distance is greater than 2 Å. Thus, no B−H interaction exists.…”

Section: Resultsmentioning

confidence: 99%

Structural and Reaction Chemistry of Tungstenocene Boryl Complexes

Hartwig

1996

Organometallics

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The structural and reaction chemistry of Cp2W(H)(Bcat) (cat = O2C6H4) (1) and Cp2W(Bcat‘)2 (cat‘ = O2C6H3-t-Bu or O2C6H2-t-Bu2) (2a,b) is reported. Compound 1 was prepared by reaction of the anion [Cp2WH]- with ClBcat, and 2a,b were prepared by oxidative addition of cat‘BBcat‘ by photochemical or thermal generation of tungstenocene. The X-ray structures of 1 and 2a are reported, and they display geometries indicating dπ−pπ interaction. The reaction chemistry of these compounds with small molecules involves protonation by alcohols, water-catalyzed protonation by amines, halogenation of the hydride in 1, and resistance toward formation of Lewis acid−base complexes. In addition, 1 undergoes photochemically induced reductive elimination of HBcat. Remarkably, generation of tungstenocene in the presence of cat‘BBcat‘ in benzene solvent led to the formation of 2 rather than oxidative addition of the solvent.

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“…The bis-η 5 -cyclopentadienyl motif, Cp 2 MF 2 (Cp = η 5 -C 5 H 5 ), fulfilled this requirement and presented a structure that can be systematically varied in terms of both central metal and substitution of the cyclopentadienyl ligands. This choice of structure favored the study of group 4 for which the desired fluorides, Cp 2 MF 2 , are well-known, − whereas analogues for groups 5 and 6 periodic series have yet to be reported. ,, …”

Section: Resultsmentioning

confidence: 99%

“…This choice of structure favored the study of group 4 for which the desired fluorides, Cp 2 MF 2 , are well-known, 61−63 whereas analogues for groups 5 and 6 periodic series have yet to be reported. 35,64,65 19 F NMR Studies of Binding. The 19 F NMR resonances for d 0 Cp 2 MF 2 compounds are located at positive or near-positive chemical shifts (Cp 2 TiF 2 δ 65.1 in CDCl 3 ) and contrast with those of group 10 that lie at far higher field (1a δ −371.4 in C 6 D 6 ).…”

Section: ■ Resultsmentioning

confidence: 99%

The Contrasting Character of Early and Late Transition Metal Fluorides as Hydrogen Bond Acceptors

et al. 2015

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The association constants and enthalpies for the binding of hydrogen bond donors to group 10 transition metal complexes featuring a single fluoride ligand (trans-[Ni(F)(2-C5NF4)(PR3)2], R = Et 1a, Cy 1b, trans-[Pd(F)(4-C5NF4)(PCy3)2] 2, trans-[Pt(F){2-C5NF2H(CF3)}(PCy3)2] 3 and of group 4 difluorides (Cp2MF2, M = Ti 4a, Zr 5a, Hf 6a; Cp*2MF2, M = Ti 4b, Zr 5b, Hf 6b) are reported. These measurements allow placement of these fluoride ligands on the scales of organic H-bond acceptor strength. The H-bond acceptor capability β (Hunter scale) for the group 10 metal fluorides is far greater (1a 12.1, 1b 9.7, 2 11.6, 3 11.0) than that for group 4 metal fluorides (4a 5.8, 5a 4.7, 6a 4.7, 4b 6.9, 5b 5.6, 6b 5.4), demonstrating that the group 10 fluorides are comparable to the strongest organic H-bond acceptors, such as Me3NO, whereas group 4 fluorides fall in the same range as N-bases aniline through pyridine. Additionally, the measurement of the binding enthalpy of 4-fluorophenol to 1a in carbon tetrachloride (-23.5 ± 0.3 kJ mol(-1)) interlocks our study with Laurence's scale of H-bond basicity of organic molecules. The much greater polarity of group 10 metal fluorides than that of the group 4 metal fluorides is consistent with the importance of pπ-dπ bonding in the latter. The polarity of the group 10 metal fluorides indicates their potential as building blocks for hydrogen-bonded assemblies. The synthesis of trans-[Ni(F){2-C5NF3(NH2)}(PEt3)2], which exhibits an extended chain structure assembled by hydrogen bonds between the amine and metal-fluoride groups, confirms this hypothesis.

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Insertion reactions of bis(η5-cyclopentadienyl)-dihydridotungsten with activated olefins and with acetylenes: Tungstenocene alkyl hydrides, olefin and acetylene complexes

Cited by 13 publications

References 36 publications

Microwave Spectra and Gas-Phase Structural Parameters of Bis(η⁵-cyclopentadienyl)tungsten Dihydride

Microwave Spectra and Gas-Phase Structural Parameters of Bis(η⁵-cyclopentadienyl)tungsten Dihydride

Structural and Reaction Chemistry of Tungstenocene Boryl Complexes

The Contrasting Character of Early and Late Transition Metal Fluorides as Hydrogen Bond Acceptors

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Insertion reactions of bis(η5-cyclopentadienyl)-dihydridotungsten with activated olefins and with acetylenes: Tungstenocene alkyl hydrides, olefin and acetylene complexes

Cited by 13 publications

References 36 publications

Microwave Spectra and Gas-Phase Structural Parameters of Bis(η5-cyclopentadienyl)tungsten Dihydride

Microwave Spectra and Gas-Phase Structural Parameters of Bis(η5-cyclopentadienyl)tungsten Dihydride

Structural and Reaction Chemistry of Tungstenocene Boryl Complexes

The Contrasting Character of Early and Late Transition Metal Fluorides as Hydrogen Bond Acceptors

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Microwave Spectra and Gas-Phase Structural Parameters of Bis(η⁵-cyclopentadienyl)tungsten Dihydride

Microwave Spectra and Gas-Phase Structural Parameters of Bis(η⁵-cyclopentadienyl)tungsten Dihydride