Reactions of Thorium Atoms with Polyhalomethanes: Infrared Spectra of the CH2=ThX2, HC÷ThX3, and XC÷ThX3 Molecules

Lyon, Jonathan T.; Andrews, Lester

doi:10.1002/ejic.200701048

Cited by 38 publications

(35 citation statements)

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“…[11][12][13][14] The reactions of groups 4 and 6 and Th metals with methylene halides give a symmetric C 2v or C s CH 2 dMX 2 product without agostic distortion, but the analogous uranium species are predicted to be distorted based on DFT calculations. [15][16][17][18] Here we report similar experiments and…”

Section: ' Introductionsupporting

confidence: 90%

Matrix Infrared Spectroscopic and Computational Investigations of the Lanthanide−Methylene Complexes CH₂LnF₂ with Single Ln−C Bonds

et al. 2011

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Laser-ablated lanthanide metal atoms were condensed with CH(2)F(2) in excess argon at 6 K or neon at 4 K. New infrared absorption bands are assigned to the oxidative addition product methylene lanthanide difluorides on the basis of deuterium substitution and vibrational frequency calculations with density functional theory (DFT). Two dominant absorptions in the 500 cm(-1) region are identified as lanthanide-fluoride stretching modes for this very strong infrared absorption. The predominantly lanthanide-carbon stretching modes follow a similar trend of increasing with metal size and have characteristic 30 cm(-1) deuterium and 14 cm(-1) (13)C isotopic shifts. The electronic structure calculations show that these CH(2)LnF(2) complexes are not analogous to the simple transition and actinide metal methylidenes with metal-carbon double bonds that have been investigated previously, because the lanthanide metals (in the +2 or +3 oxidation state) do not appear to form a π-type bond with the CH(2) group. The DFT and ab initio correlated molecular orbital theory calculations predict that these complexes exist as multiradicals, with a Ln-C σ bond and a single electron on C-2p weakly coupled with f(x) (x = 1 (Ce), 2 (Pr), 3(Nd), etc.) electrons in the adjacent Ln-4f orbitals. The Ln-C σ bond is composed of about 15% Ln-5d,6s and 85% C-sp(2) hybrid orbital. The Ln orbital has predominantly 6s and 5d character with more d-character for early lanthanides and increasing amounts of s-character across the row. The Ln-F bonds are almost purely ionic. Accordingly, the argon-neon matrix shifts are large (13-16 cm(-1)) for the ionic Ln-F bond stretching modes and small (∼1 cm(-1)) for the more covalent Ln-C bond stretching modes.

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Section: ' Introductionsupporting

confidence: 90%

Matrix Infrared Spectroscopic and Computational Investigations of the Lanthanide−Methylene Complexes CH₂LnF₂ with Single Ln−C Bonds

et al. 2011

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“…This combined approach does not only allow to probe systems for agostic interactions it also provides a valuable tool for the often difficult identification of compounds in matrix IR. By computational comparison of different isotopomers it was also possible to estimate the strength of the agostic interaction [95] or to eliminate possible candidates for agostic interactions [102,103]. In order to achieve this IRC calculations were used to follow the structure from one minimum to the other.…”

Section: Vibrational Constantsmentioning

confidence: 99%

Characterization of agostic interactions in theory and computation

Lein

2009

Coordination Chemistry Reviews

151

108

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Agostic interactions are covalent intramolecular interactions between an electron deficient metal and a sigma-bond in close geometrical proximity to the metal atom. While the classic cases involve CH sigma-bonds close to early transition metals like titanium, many more agostic systems have been proposed which contain CH, SiH, BH, CC and SiC sigma-bonds coordinated to a wide range of metal atoms. Recent computational studies of a multitude of agostic interactions are reviewed in this contribution. It is highlighted how several difficulties with the theoretical description of the phenomenon arise because of the relative weakness of this interaction. The methodology used to compute and interpret agostic interactions is presented and different approaches such as atoms in molecules (AIM), natural bonding orbitals (NBO) or the electron localization function (ELF) are compared and put into context. A brief overview of the history and terminology of agostic interactions is given in the introduction and fundamental differences between alpha, beta; and other agostic interactions are explained.Comment: 24 pages, 10 figures, 109 references. Submitted to Coordination Chemistry Review

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“…Thorium–ligand multiple bond chemistry is an attractive area for studying chemical bonding because of the intrinsic features of metal–ligand multiple bonds, but it is far less developed than uranium1234, being restricted to a few carbene21252627282930, imido313233 and chalcogenido222324343536 complexes. Very recently the first thorium–phosphinidene and μ-phosphido complexes under ambient conditions37 added to the preparation of a thorium–phosphido complex in frozen argon matrix isolation conditions38.…”

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Triamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs

et al. 2017

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Despite a major expansion of uranium–ligand multiple bond chemistry in recent years, analogous complexes involving other actinides (An) remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, phosphorus and chalcogenides are reported, and none to arsenic are known; indeed only two complexes with thorium–arsenic single bonds have been structurally authenticated, reflecting the challenges of stabilizing polar linkages at the large thorium ion. Here, we report thorium parent–arsenide (ThAsH2), –arsinidiides (ThAs(H)K and ThAs(H)Th) and arsenido (ThAsTh) linkages stabilized by a bulky triamidoamine ligand. The ThAs(H)K and ThAsTh linkages exhibit polarized-covalent thorium–arsenic multiple bonding interactions, hitherto restricted to cryogenic matrix isolation experiments, and the AnAs(H)An and AnAsAn linkages reported here have no precedent in f-block chemistry. 7s, 6d and 5f orbital contributions to the Th–As bonds are suggested by quantum chemical calculations, and their compositions unexpectedly appear to be tensioned differently compared to phosphorus congeners.

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Reactions of Thorium Atoms with Polyhalomethanes: Infrared Spectra of the CH₂=ThX₂, HC÷ThX₃, and XC÷ThX₃ Molecules

Cited by 38 publications

References 32 publications

Matrix Infrared Spectroscopic and Computational Investigations of the Lanthanide−Methylene Complexes CH₂LnF₂ with Single Ln−C Bonds

Matrix Infrared Spectroscopic and Computational Investigations of the Lanthanide−Methylene Complexes CH₂LnF₂ with Single Ln−C Bonds

Characterization of agostic interactions in theory and computation

Triamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs

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Reactions of Thorium Atoms with Polyhalomethanes: Infrared Spectra of the CH2=ThX2, HC÷ThX3, and XC÷ThX3 Molecules

Cited by 38 publications

References 32 publications

Matrix Infrared Spectroscopic and Computational Investigations of the Lanthanide−Methylene Complexes CH2LnF2 with Single Ln−C Bonds

Matrix Infrared Spectroscopic and Computational Investigations of the Lanthanide−Methylene Complexes CH2LnF2 with Single Ln−C Bonds

Characterization of agostic interactions in theory and computation

Triamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs

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Product

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Reactions of Thorium Atoms with Polyhalomethanes: Infrared Spectra of the CH₂=ThX₂, HC÷ThX₃, and XC÷ThX₃ Molecules

Matrix Infrared Spectroscopic and Computational Investigations of the Lanthanide−Methylene Complexes CH₂LnF₂ with Single Ln−C Bonds

Matrix Infrared Spectroscopic and Computational Investigations of the Lanthanide−Methylene Complexes CH₂LnF₂ with Single Ln−C Bonds