Matrix Photochemistry Of Transition Metal Complexes: Principles, Applications and Links to Other Methods

Perutz, Robin N.

doi:10.1007/978-94-009-0281-7_3

Cited by 2 publications

(2 citation statements)

References 76 publications

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“…Metal carbonyls are best known for their complexes with transition metals (TM), which have numerous applications like industrial catalysts or precursors for exotic compounds. They were extensively studied in the 1970s, using mostly matrix isolation trapping, spectroscopy and photochemical excitation [1][2][3][4][5][6][7], resulting in substantial amounts of experimental physicochemical data.…”

Section: Introductionmentioning

confidence: 99%

Preference of C2v Symmetry in Low-Spin Hexacarbonyls of Rare-Earth and f Elements

Kovács,

Klotzbücher

2024

Symmetry

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The structures and bonding of selected neutral M(CO)6 complexes (M = Sc, Y, La, Lu, Ac and U) have been studied by density functional theory calculations. The calculations revealed the preference for C2v symmetry and low-spin electronic state for most of these complexes. The relative stability of the low-symmetry species increases gradually with the size of the metal atom. While the characteristic Oh hexa-coordinated structure is favored in the high-spin electronic state of the smaller metals, for heavier metals, important advantages of the C2v vs. Oh structures include larger charge transfer interactions in terms of transferred electrons as well as better steric conditions. Our joint experimental–theoretical analysis detected and confirmed the Oh structure of the Sc(CO)6 complex in cryogenic CO/Ar matrices.

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Section: Introductionmentioning

confidence: 99%

Preference of C2v Symmetry in Low-Spin Hexacarbonyls of Rare-Earth and f Elements

Kovács,

Klotzbücher

2024

Symmetry

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“…Within a few years, binary stable and unstable species of most of the transition metals (TM) were discovered by one of two routes: either the trapping of unstable intermediates after the photochemical reaction of a stable precursor in inert matrices or the direct formation of species of interest by the direct reaction of “naked” metal atoms with CO molecules diluted in inert gas mixtures prior to freeze-out on a matrix window. Techniques and discovered complexes have been topics in numerous articles, reviews, and books [ 3 , 4 , 5 , 6 ].…”

Section: Introductionmentioning

confidence: 99%

A DFT and Matrix–Isolation IR/UV-Visible Study of High-Coordinated Lanthanide-CO Complexes

Kovács

Klotzbücher²

2023

Molecules

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Recent joint mass spectrometric and IR photodissociation studies have provided proof on the existence of octa-coordinated ionic lanthanide-carbonyl complexes under those extreme gaseous conditions. In contrast, in older literature concerning cryogenic studies of neutral Ln(CO)x species, the highest coordination was assigned to hexa-coordinated Ln(CO)6 molecules. The present study aims to clarify the above controversy using matrix isolation spectroscopy and DFT calculations. In order to ensure the maximum possible coordination, the Ln(CO)x complexes were synthesized in neat CO cryogenic matrices at 10 K and were investigated by infrared and UV-visible spectroscopy. The formed complexes were identified on the basis of the characteristic CO stretching frequencies of the ground-state molecules predicted by DFT calculations. Our joint experimental–theoretical analysis confirmed the preference of octa-coordinated Ln(CO)8 complexes in cryogenic neat CO matrices.

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Matrix Photochemistry Of Transition Metal Complexes: Principles, Applications and Links to Other Methods

Cited by 2 publications

References 76 publications

Preference of C2v Symmetry in Low-Spin Hexacarbonyls of Rare-Earth and f Elements

Preference of C2v Symmetry in Low-Spin Hexacarbonyls of Rare-Earth and f Elements

A DFT and Matrix–Isolation IR/UV-Visible Study of High-Coordinated Lanthanide-CO Complexes

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