The infrared and Raman spectra of π-cyclopentadienyl compounds: Cyclopentadienyl-manganese-thearbonyl

Hyams, I.J.; Bailey, R. T.; Lippincott, Ellis R.

doi:10.1016/0584-8539(67)80230-7

Cited by 59 publications

(9 citation statements)

References 28 publications

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“…In addition, the very intense peaks at 1960 and 2036 cm –1 are quite characteristic of this type of carbonyl complexes . Finally, our spectrum is similar to those reported for MeCpMn(CO) 3 in the liquid and solid phases …”

Section: Resultssupporting

confidence: 87%

Kinetics of Adsorption of Methylcyclopentadienyl Manganese Tricarbonyl on Copper Surfaces and Implications for the Atomic Layer Deposition of Thin Solid Films

Bouman

Zaera

2016

J. Phys. Chem. C

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The kinetics of the thermal chemistry of methylcyclopentadienyl manganese tricarbonyl on copper surfaces was followed by infrared absorption spectroscopy analysis of the gas surrounding the substrate. Dissociative adsorption of the MeCpMn(CO)3 precursor was seen at low temperatures, below 400 K, and was determined to occur via the initial loss of a single carbon monoxide ligand. Full decarbonylation was observed starting at a surface temperature of approximately 510 K, and full decomposition of the Mn precursor was seen to be complete by 540 K. All these transitions were determined to occur at temperatures at least 100 K lower than those reported on silicon oxide surfaces. Comparison with reference spectra afforded the identification of the main hydrocarbon product as a mixture of methylcyclopentadiene isomers. Isothermal measurements of MeCpMn(CO)3 partial pressure versus reaction time highlighted a deviation from first-order kinetics, an effect associated with changes in surface reactivity. A self-limiting regime typical of atomic layer deposition processes was identified between 475 and 525 K by the incomplete conversion of the precursor, which displayed similar reaction rate and reached the same asymptotic partial pressure at all temperatures within that temperature bracket. Higher surface temperatures promoted total precursor consumption, at a rate that increased with increasing surface temperature; an apparent activation energy of approximately 40 kJ/mol was estimated in that high-temperature regime. The resulting chemical-vapor deposited multilayers were identified by X-ray photoelectron spectroscopy to consist of MnO.

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Section: Resultssupporting

confidence: 87%

Kinetics of Adsorption of Methylcyclopentadienyl Manganese Tricarbonyl on Copper Surfaces and Implications for the Atomic Layer Deposition of Thin Solid Films

Bouman

Zaera

2016

J. Phys. Chem. C

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“…The other two bands, close to the strong totally symmetric ones, can be attributed to modes 11′ and 18′, the intermediate being probably e 1 , because of the essentially coincidence with a corresponding infrared absorption. Some marginally different assignments 22,24,26 may be ruled out, because of the general pattern similarity, a pattern, interestingly, also found in the spectra of (pyrrolyl)Mn(CO) 3 . 26 A strong band in the CpFe(CO) 2 X spectra, moving toward lower frequency as the mass of X increases, is clearly the ν(Fe-X) mode.…”

Section: Resultsmentioning

confidence: 94%

“…Of these, e 1 mode can be regarded as a ring tilt relative to the local C 5 axis and the e 2 mode has out-of-plane ring deformation character. The symmetric stretch a 1 (4′) for CpM(CO) 3 complexes is surely at 353 and at 327 cm -1 when M ) Mn 22,24,26 or Re, 23 straightforward for the other complexes. The other two bands, close to the strong totally symmetric ones, can be attributed to modes 11′ and 18′, the intermediate being probably e 1 , because of the essentially coincidence with a corresponding infrared absorption.…”

Section: Resultsmentioning

confidence: 95%

“…The molecular symmetries are different and generally low, but the fragment CpM can be treated on the basis of the local C 5v symmetry. This assumption is usually accepted − and implies the exclusion of any coupling between the vibrations of the CpM fragment and of the L n fragment. This is clearly unacceptable as far as skeletal modes are concerned, but it may be valid for the intraring vibrations, which, as we have seen, are essentially uncoupled, even between two identical Cp rings.…”

Section: Resultsmentioning

confidence: 99%

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Vibrational Study of (η⁵-Cyclopentadienyl)metal Complexes

et al. 1997

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Raman and infrared spectral data on the vibrational modes of the M-(η 5 -C 5 H 5 ) unit have been collected and the fundamental assignments revisited. Complexes belonging to the metallocene series M(η 5 -C 5 H 5 ) and the cyclopentadienide salts [η 5 -C 5 H 5 -][M + ] have been studied, together with some monometallic (η 5 -C 5 H 5 )ML n and bimetallic (η 5 -C 5 H 5 ) 2 M 2 L 2n compounds. Comparison of the spectra shows a common vibrational pattern of the intraring modes, with minor variations in frequency and intensity, which allows the establishment of a vibrational fingerprint of general validity. Raman spectra give rise to a firm assignment of the skeletal metal-ring modes; a correlation is noted between the metal-ring stretch force constant and the metal-carbon distance. The approximate CH out-of-plane force constants vary considerably and presumably reflect different H-ring electrostatic repulsions.

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“…2 The infrared and Raman spectra of many sandwich and halfsandwich compounds have been investigated, providing information about the fundamental transitions in these molecules. The normal mode symmetry of sandwich compounds has been studied, 3 and the infrared spectra of gaseous, 4 solution, 5 and solid 7 ferrocene; gaseous 4 and solution 5 ruthenocene; solid manganocene; 6,7 solid chromocene; 7 and gaseous, liquid, and solid cyclopentadienyl manganese tricarbonyl [9][10][11][12] can be found in the literature. In addition, the Raman spectra 8 of manganocene and chromocene were reported.…”

Section: Introductionmentioning

confidence: 99%

Vibrational Overtone Spectroscopy of Metallocenes and “Half-Sandwich” Organometallic Complexes

Fedorov

Snavely

1999

J. Phys. Chem. A

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The FTIR spectra of ferrocene, ruthenocene, cyclopentadienyl manganese tricarbonyl (CPMT), cyclopentadienyl titanium trichloride (CPTT), and cyclopentadienyl iron dicarbonyl iodide (CPIDI) CCl4 solutions are presented at the first and second overtone region (Δv = 2, 3). The gaseous ferrocene, ruthenocene, and CPMT spectra are also presented at the third overtone region (Δv = 4) recorded by intracavity photoacoustic spectroscopy. Assignments for the observed transitions are suggested for the liquid and reevaluated for the gas-phase spectra. The influence of the metal and other ligands attached to the metal on the vibrational behavior of the cyclopentadienyl ring is also discussed.

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The infrared and Raman spectra of π-cyclopentadienyl compounds: Cyclopentadienyl-manganese-thearbonyl

Cited by 59 publications

References 28 publications

Kinetics of Adsorption of Methylcyclopentadienyl Manganese Tricarbonyl on Copper Surfaces and Implications for the Atomic Layer Deposition of Thin Solid Films

Kinetics of Adsorption of Methylcyclopentadienyl Manganese Tricarbonyl on Copper Surfaces and Implications for the Atomic Layer Deposition of Thin Solid Films

Vibrational Study of (η⁵-Cyclopentadienyl)metal Complexes

Vibrational Overtone Spectroscopy of Metallocenes and “Half-Sandwich” Organometallic Complexes

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The infrared and Raman spectra of π-cyclopentadienyl compounds: Cyclopentadienyl-manganese-thearbonyl

Cited by 59 publications

References 28 publications

Kinetics of Adsorption of Methylcyclopentadienyl Manganese Tricarbonyl on Copper Surfaces and Implications for the Atomic Layer Deposition of Thin Solid Films

Kinetics of Adsorption of Methylcyclopentadienyl Manganese Tricarbonyl on Copper Surfaces and Implications for the Atomic Layer Deposition of Thin Solid Films

Vibrational Study of (η5-Cyclopentadienyl)metal Complexes

Vibrational Overtone Spectroscopy of Metallocenes and “Half-Sandwich” Organometallic Complexes

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Vibrational Study of (η⁵-Cyclopentadienyl)metal Complexes