Cryochemical studies. 3. ESR studies of the reaction of Group IB metal atoms with acetylene and phenylacetylene in a rotating cryostat

Chenier, J. H. B.; Howard, Judith A. K.; Mile, B.; Sutcliffe, R.

doi:10.1021/ja00342a023

Cited by 55 publications

(40 citation statements)

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“…The relative stabilities of the vinyl and ncomplex of CuC2H2, and of structures 4 and ( 5 6 ) ,of C U~C~H~, are probably similar but with some extra stability for the n-complex of Cu2C2H2 [on account of greater Cu(4p) participation]. The experimental observation of vinyl AgC2H2 and AuC2H2 [22] and the bond dissociation energies of the dimers ( C U~: 2.03 eV; Ag2: 1.66 eV; and A u~: 2.30 eV) [25] indicate that metal-metal bond breaking upon reaction with acetylene is even more likely to occur for Ag2 than for Cu2.…”

Section: Cu C Hzmentioning

confidence: 93%

“…Vinyl structures have been observed in the cases of AgC2H2 and AuC2H2 [22], but the ESR spectra for copper atoms and acetylene cocondensed in matrix implies a C2" C U C~H~ Tcomplex [22,23]. The fact that gold and silver, but not copper, are seen to form vinyl structures in matrix cocondensation experiments suggests that the relative stability of the vinyl and T- bonded structures depends on subtle effects.…”

Section: Cu C Hzmentioning

confidence: 99%

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Bonding of acetylene to copper atom, dimer, and trimer

Fournier¹

1994

Int J of Quantum Chemistry

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The bonding of acetylene to copper atom, dimer, and trimer was investigated with a Kohn-Sham density functional approach. Full geometry optimization yielded the equilibrium structures of various CunC2H2 species. Gradient corrections were included in the calculation of binding energies (BE). The C U -C~H~ complex was found to have a C, structure and a BE of 10 kcal/mol. Three isomers of CuzC2Hz have similar total energies: a CzU end-bonded structure with a BE of 18 kcal/mol, and two 1,2-dicupro ethylene isomers-a cis form with a BE of 12 kcal/mol and a trans form with a BE of 15 kcal/mol. Two stable CzV isomers of C U~C~H~ were found. In both isomers, the Cu3 ring relaxes from its isosceles structure, with two short bonds (2.247 A) and one long bond (2.478 A), and adopts a nearly equilateral geometry. In one isomer of C U~C~H~, the acetylene is bonded to one apex of the Cu3 ring with a BE of 29 kcal/mol. In the other, it is bonded to two copper atoms of one side of the Cu3 ring with a BE of 33 kcal/mol.

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Section: Cu C Hzmentioning

confidence: 93%

Section: Cu C Hzmentioning

confidence: 99%

Bonding of acetylene to copper atom, dimer, and trimer

Fournier¹

1994

Int J of Quantum Chemistry

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“…A number of metal atom reactions with acetylene have already been studied. [12][13][14][15] Aluminium adducts with acetylene have been examined using ab initio calculations, and a number of stable Al-C 2 H 2 isomers have been predicted. [16][17][18] The related reaction between laser ablated Al atoms and acetylene has been examined using IR matrix isolation spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Gas phase electronic spectrum of linear AlCCH

Apetrei

Ding

Maier

2007

Phys. Chem. Chem. Phys.

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The electronic spectrum of the aluminium containing species AlCCH has been detected in the gas phase in the region 315-355 nm. The experiment used a mass selective resonant two-color two-photon ionization technique coupled to a laser ablation source. Structures of the AlCCH isomers have been optimized using density functional theory (DFT) and the excitation energies to the low-lying electronic excited states calculated. Based on the analysis of the observed rotational structure and the theoretical data, the spectrum is assigned to the A (1)Pi<-- X (1)Sigma(+) electronic transition of linear AlCCH. The vibronic band system is complicated by the Renner-Teller effect in the excited state. The assignment yields nu(4)'' = 516.4 cm(-1) for the stretching mode in the ground X (1)Sigma(+) state and nu(4)' = 654.5 cm(-1) for A (1)Pi excited state. Molecular constants determined from the rotational analysis are B(0)'' = 0.16487(14), B(0)' = 0.17845(13) and T(0) = 28 755.04 cm(-1). The experimental and theoretical data indicate a shorter Al-C bond in the A (1)Pi excited than the X (1)Sigma(+) ground state.

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“…Complexes of zero valent gold (in the form of atoms or at the surface of the bulk metal) and unsaturated molecules such as alkenes 375,376 , alkynes 376,377 , allenes 378 , arenes 379 or fullerenes 380 were the subject of a number of experimental studies. Molecular species which are formed by low-temperature cocondensation of gold atoms with unsaturated organic substrates have been characterized by their infrared/Raman, UVvisible absorption and ESR spectra, but the interpretation of these data is not without contradictions 377,378,381 .…”

Section: Synthesis and Properties Of Alkene Alkyne Carbene And mentioning

confidence: 99%

“…Molecular species which are formed by low-temperature cocondensation of gold atoms with unsaturated organic substrates have been characterized by their infrared/Raman, UVvisible absorption and ESR spectra, but the interpretation of these data is not without contradictions 377,378,381 .…”

Section: Synthesis and Properties Of Alkene Alkyne Carbene And mentioning

confidence: 99%