Semiempirical molecular orbital calculations. V. Electronic structure of arenechromium tricarbonyls and chromium hexacarbonyl

Carroll, D. G.; McGlynn, S. P.

doi:10.1021/ic50065a004

Cited by 92 publications

(20 citation statements)

References 4 publications

(6 reference statements)

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“…Linear Optical Properties of the Complexes 1, 3, and 6 ( Electronic Spectra and Solvochromicity). In the UV/vis spectra of the alkynylated ( 1 and 3 ) and the alkenylated complexes ( 6 ) recorded in chloroform, the appearance of the intense longest wavelength absorption band between 378 ( 1f ) and 488 nm ( 6g ) can be assigned to the metal-to-ligand charge-transfer (MLCT) band arising from a charge transition from the chromium center to the π- and σ-bound ligands. , The next band between 309 ( 1b ) and 383 nm ( 6f ) is the most intense absorption and arises from intraligand (IL) transitions with high oscillator strength, to the most extent from π−π* transitions . This rationale is also supported by the inspection of the solvochromicities of these complexes.…”

Section: Resultsmentioning

confidence: 99%

Syntheses and NLO Properties of Chromium Carbonyl Arene Complexes with Conjugated Side Chains: The Amphoteric Nature of Chromium Carbonyl Complexation in Push−Pull Chromophores

Müller¹,

Netz²,

Ansorge³

et al. 1999

Organometallics

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Donor- and acceptor-substituted alkynylated chromium carbonyl arene complexes Cr(CO)2L(η 6-R1-C6H4)(C⋮C) n R2 (1, n = 1, L = CO, PPh3, R1 = H, o-formyl, R2 = p-C6H4-NMe2, p-C6H4-NO2, ferrocenyl; 3, n = 2, L = CO, R1 = H, R2 = p-C6H4-NMe2, p-C6H4-NO2, ferrocenyl) are easily accessible by Sonogashira alkynylations of chloroarene complexes and Cadiot−Chodkiewicz couplings of bromoalkynes with the complexed phenyl acetylene 1a (n = 1, L = CO, R1 = R2 = H), respectively. The Horner−Emmons−Wadsworth olefinations of the Cr(CO)3-complexed benzylphosphonate and (hetero)aromatic aldehydes give rise to numerous alkenylated chromium carbonyl arene complexes (E) n -Cr(CO)3(η 6-C6H5)(CHCH) n R1 (6, n = 1−3, R1 = p-C6H4-NMe2, p-C6H4-NO2, 2-(4-nitrothienyl)). The linear (UV/vis spectra) and the nonlinear optical properties (hyper Rayleigh scattering measurements) of the complexes 1, 3, and 6 reveal that the chromium carbonyl arene fragment behaves electronically amphoteric, i.e., as an electron donor or electron acceptor depending on the substituent on the far end of the conjugating bridge. The first hyperpolarizability β-values ( = (8−41) × 10-30 esu) are found to be similar to those of related ferrocenyl compounds.

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Section: Resultsmentioning

confidence: 99%

Syntheses and NLO Properties of Chromium Carbonyl Arene Complexes with Conjugated Side Chains: The Amphoteric Nature of Chromium Carbonyl Complexation in Push−Pull Chromophores

Müller¹,

Netz²,

Ansorge³

et al. 1999

Organometallics

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“…Such an interaction seems plausible if one considers the probable ground state charge distribution within the Fe-CO unit. For a variety of metal carbonyls, significant amounts of positive charge have been calculated to be localized on the carbonyl carbon atoms (Fenske & DeKoch, 1970;Caulton & Fenske, 1968; Schreiner & Brown, 1968; Carroll & McGlynn, 1968). Indeed nucleophilic attack on such an electrophilic carbon has been observed in transition metal carbonyls (Darensbourg & Darensbourg, 1970), and in ferric porphyrin-bis(cyanide) complexes (La Mar, 1977).…”

Section: Discussionmentioning

confidence: 99%

Spectroscopic studies of the nature of ligand bonding in carbonmonoxyhemoglobins: evidence of a specific function for histidine-E7 from infrared and nuclear magnetic resonance intensities

Satterlee¹,

Teintze²,

Richards³

1978

Biochemistry

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Infrared spectra of carbon monoxide ligated hemoglobins from human, horse, and rabbit donors have been examined. A single vibrational frequency at 1951 cm-1 is observed for CO bound to the heme in horse and human hemoglobins. Studies of the isolated alpha-CO and beta-CO subunits of human hemoglobin reveal that the observation of a single frequency in the intact tetramer is the result of a superposition of the alpha-CO and beta-CO vibrational frequencies. The apparent integrated absorption intensities of these CO vibrations are shown both to have values of 1.0 X 10(5)M-1cm-2 within experimental error. For rabbit CO-Hb two vibrational frequencies appear (Caughey, W. S., et al. (1973) Fed. Proc., Fed. Am. Soc. Exp. Biol. 32, 552) and are assigned to CO bound to the beta (1951 cm-1) and alpha(1928 cm-1) subunits within the intact tetramer. The beta-CO subunit exhibits both frequency and intensity similarities with horse and human hemoglobins. The rabbit alpha-CO subunit, however, exhibits a markedly lower frequency and much smaller intensity compared with the other CO-hemoglobins. These data are interpreted in terms of a specific role for the distal histidine (E7) in rabbit alpha subunits, in which this histidine functions as a nucleophilic donor to coordinated CO.

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“…There is much compelling evidence from reactivity data (1-7), dipole moment measurements (8), molecular orbital calculations (9), and n.m.r. chemical shifts (10)(11)(12)(13) to suggest that the Cr(CO), group is strongly electron-withdrawing, perhaps comparable to apara-nitro group.…”

Section: Introductionmentioning

confidence: 99%

The Question of σ Participation in the Bonding of Fluorosubstituted Arenes to Chromium Tricarbonyl. A ¹⁹F Nuclear Magnetic Resonance Investigation

Fletcher¹,

McGlinchey²

1975

Can. J. Chem.

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I9F n.m.r. chemical shifts of free fluoroarenes have been correlated with the Swain–Lupton field and resonance parameters. Comparison of these data with the corresponding Cr(CO)3 complexes shows little change in the transmission of mesomeric effects by para-substituents. Meta-substituents which interact primarily by a field effect have very little influence on the fluorine chemical shift in the complexes suggesting that the σ framework of the ring interacts with the chromium.

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Semiempirical molecular orbital calculations. V. Electronic structure of arenechromium tricarbonyls and chromium hexacarbonyl

Cited by 92 publications

References 4 publications

Syntheses and NLO Properties of Chromium Carbonyl Arene Complexes with Conjugated Side Chains: The Amphoteric Nature of Chromium Carbonyl Complexation in Push−Pull Chromophores

Syntheses and NLO Properties of Chromium Carbonyl Arene Complexes with Conjugated Side Chains: The Amphoteric Nature of Chromium Carbonyl Complexation in Push−Pull Chromophores

Spectroscopic studies of the nature of ligand bonding in carbonmonoxyhemoglobins: evidence of a specific function for histidine-E7 from infrared and nuclear magnetic resonance intensities

The Question of σ Participation in the Bonding of Fluorosubstituted Arenes to Chromium Tricarbonyl. A ¹⁹F Nuclear Magnetic Resonance Investigation

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Semiempirical molecular orbital calculations. V. Electronic structure of arenechromium tricarbonyls and chromium hexacarbonyl

Cited by 92 publications

References 4 publications

Syntheses and NLO Properties of Chromium Carbonyl Arene Complexes with Conjugated Side Chains: The Amphoteric Nature of Chromium Carbonyl Complexation in Push−Pull Chromophores

Syntheses and NLO Properties of Chromium Carbonyl Arene Complexes with Conjugated Side Chains: The Amphoteric Nature of Chromium Carbonyl Complexation in Push−Pull Chromophores

Spectroscopic studies of the nature of ligand bonding in carbonmonoxyhemoglobins: evidence of a specific function for histidine-E7 from infrared and nuclear magnetic resonance intensities

The Question of σ Participation in the Bonding of Fluorosubstituted Arenes to Chromium Tricarbonyl. A 19F Nuclear Magnetic Resonance Investigation

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The Question of σ Participation in the Bonding of Fluorosubstituted Arenes to Chromium Tricarbonyl. A ¹⁹F Nuclear Magnetic Resonance Investigation