Mass spectra of monohapto-cyclopentadienyl derivatives of group IVB elements

Ustynyuk, Yu. A.; Zakharov, P. I.; Азизов, А. А.; Potapov, V. K.; Pribytkova, I. M.

doi:10.1016/s0022-328x(00)89329-8

Cited by 21 publications

(3 citation statements)

References 8 publications

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“…This was rationalized in terms of the fact that the E−C(η 1 -Cp) bond, where E = main group elements, is more readily cleaved as E becomes heavier . On the other hand, both experimentally − and theoretically, it was corroborated that there exists an excellent correlation between the rate of 1,5-shift and the degree of σ−π hyperconjugation (delocalization of the E−C(η 1 -Cp) σ bond to adjacent π* orbitals on η 1 -Cp).…”

Section: Introductionmentioning

confidence: 90%

Mechanistic Studies of Ligand Fluxionality in [M(η⁵-Cp)(η¹-Cp)(L)₂]ⁿ

2009

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Density functional theory has been used to provide a thorough investigation of the mechanistic factors affecting Cp ligand fluxionality in a series of organometallic complexes, [M(eta(5)-Cp)(eta(1)-Cp)(L)(2)](n), involving different metals, different oxidation states, and different ligands. Excellent agreement with experiment for the barrier heights for the 1,5-shift were obtained for the complexes [Fe(eta(5)-Cp*)(eta(1)-Cp)(CO)(2)] and [Fe(eta(5)-Cp)(eta(1)-Cp)(CO)(2)]. For the range of complexes studied, the barriers have been successfully rationalized in terms of hyperconjugation, metal-Cp bond strength, and steric effects. In addition, the eta(1)-eta(5) interconversion of the Cp binding mode is shown to be a high-energy process, consistent with experimental observations. The L substitution reactions by eta(1)-Cp are quite sensitive to the nature of the metal center and ancillary ligand. A detailed theoretical explanation of the factors involved in all of these transformations is provided.

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Section: Introductionmentioning

confidence: 90%

Mechanistic Studies of Ligand Fluxionality in [M(η⁵-Cp)(η¹-Cp)(L)₂]ⁿ

2009

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“…Ir (film) 3060 (w), 2975 (m), 2915 (w), 1595 (m), 1465 (s), 1460 (s), 1435 (s), 1258 (m), 1200 (s), 1190 (s), 1105 (m), 1055 (m), 824 (m), 814 (m), 755 (s), and 727 cm-1 (m). GLC-mass spectra (70 eV) showed the expected spectra for 431 and for 5: m/e (rel intensity) 260 (0.96), 258 (0.67), 245 (100), 243 (74), 241 (45), 239 (2), 237 (3), 227 (18), 225 (13), 223 (8), 215 (13), 213 (10), 211 (7), 210 (13), 208 (9), 206 (5), 197 (7), 195 (5), 193 (3), 169 (8), 167 (6), 165 (4), 139 (35), 137 (26), 135 (23), 96 (5), and 95 (2).…”

Section: Methodsmentioning

confidence: 81%

Additions and cycloadditions of cyclopentadienylmetal compounds to benzyne

Buske¹,

Ford²

1976

J. Org. Chem.

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“…At temperatures above -10C, 3a-c rearranges to the mixtures of vinylic boranes 3d-g and 3i-j ( Figure 1). Spectroscopic studies of cyclopenta-2,4-dienylborane such as 1 H NMR, 13 C NMR, mass spectrometer and IR indicated that metallotropic shifts in solution state occurred much faster compared with prototropic shifts to give allylic isomers, which are nonfluxional [3][4][5][6][7][8][9][10] . The isolobal principle in organometallic chemistry has been reported earlier 11 .…”

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confidence: 99%