Carbon K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory Examination of Metal–Carbon Bonding in Metallocene Dichlorides

Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.; Boland, Kevin S.; Kozimor, Stosh A.; Martin, Richard L.; Shuh, David K.; Tyliszczak, Tolek; Vernon, Louis J.

doi:10.1021/ja405844j

Cited by 48 publications

(63 citation statements)

References 90 publications

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“…To evaluate the possible changes in Pd–P covalency in solution and the solid‐state, we performed dispersion‐corrected DFT and TDDFT calculations on 1 – 3 with a polarizable continuum model to simulate the CH 2 Cl 2 solution. The B3LYP functional was again selected because it has been shown to be remarkably accurate in the simulation of experimental XAS spectra via time‐dependent density functional theory (TDDFT) , , , , , , . For consistency, TDDFT calculations for 1 – 3 from our previous study were recalculated with dispersion corrections for comparison to the dispersion‐corrected solution calculations presented here.…”

Section: Resultsmentioning

confidence: 99%

Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl₂ Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

et al. 2018

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Here we report P K-edge X-ray absorption spectroscopy (XAS), density functional theory (DFT), and time-dependent density functional theory (TDDFT) studies of [R 2 P(CH 2 ) n PR 2 ]PdCl 2 , where R = phenyl or cyclohexyl and n = 1-3. P K-edge XAS data were collected on room temperature CH 2 Cl 2 solutions of [Ph 2 P(CH 2 ) n PPh 2 ]PdCl 2 , where n = 1 (dppm; 1), 2 (dppe; 2), or 3 (dppp; 3) to determine if solid-state variations in covalent Pd-P bonding reported previously (Inorg. Chem. 2015, 54, 5646) were present in solution. A flow cell was used to overcome challenges associated with photon-induced decomposition, which often occurs rapidly in solution during ligand K-edge XAS data collection at room temperature. While [a]

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Section: Resultsmentioning

confidence: 99%

Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl₂ Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

et al. 2018

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“…[39,40] In particular, we have learned that transition intensities in the f-f bands of many uranium complexes are dramatically enhanced from covalent bonding interactions and from coupling of the other low-lying electronic excitations (e.g., MLCT excited states) to the f-f transitions to engender dipole-allowed character. [41][42][43] For example, the molar extinction coefficients for f-f bands in uranium(IV) organometallic complexes have been found to range from <<10 M -1 cm -1 in non-covalent metal-ligand systems like (C 5 Me 5 ) 2 UCl 2 to ~500 M -1 cm -1 in covalent metal-ligand systems like ketimide complexes such as (C 5 Me 5 ) 2 U(-N=CPh 2 ) 2 . [34,[44][45][46][47] The electronic spectral behavior of the metallacyclocumulene systems (C 5 Me 5 ) 2 An( 4 -1,2,3,4-PhC 4 Ph) (An = Th, U) reported here diverges from that observed for most other Th and U organoactinide systems we have investigated in two ways.…”

Section: Optical Characterization Of the Metallacyclocumulene Complexmentioning

confidence: 99%

Synthesis and characterization of a new and electronically unusual uranium metallacyclocumulene, (C5Me5)2U(η4-1,2,3,4-PhC4Ph)

Pagano¹,

Erickson²,

Scott³

et al. 2017

Journal of Organometallic Chemistry

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A new uranium metallacyclocumulene, (C 5 Me 5) 2 U(η 4-PhC 4 Ph), was synthesized by both reaction of (C 5 Me 5) 2 UCl 2 with 1,4-diphenylbutadiyne in the presence of KC 8 and by ligand exchange between (C 5 Me 5) 2 U(η 2-Me 3 SiC 2 SiMe 3) and 1,4-diphenylbutadiyne. Full characterization of (C 5 Me 5) 2 U(η 4-PhC 4 Ph) is reported, including the solid-state structure. (C 5 Me 5) 2 U(η 4-PhC 4 Ph) displays an unusually detailed UV-visible spectrum, which is rare for uranium(IV) metallocene complexes. t Bu 3 H 2) 2 Th(η 2-1,2-PhC 2 Ph) and (C 5 Me 5) 2 U(η 2-1,2-Me 3 SiC 2 SiMe 3).[20-23] In related work, the Meyer group reported that the uranium(III) complex [((Ad ArO) 3 N)U III (DME)] reacts with the terminal alkynes 1-hexyne or 4-t butyl-phenylacetylene,

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“…This is especially true if future studies validate the generality of the conclusions described here on how M–E electronic structure and orbital mixing vary as the metal identity changes. Hence, our efforts will continue to focus on evaluating M–O vs. M–S bonding in both the solution- and solid-state for even heavier metals, namely lanthanide and actinide elements, 41,58,59,83,85,87 where f- and d-orbital contributions to covalency are anticipated.…”

Section: Outlook and Conclusionmentioning

confidence: 99%

Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M–S bonding for MS₄²⁻(M = Cr, Mo, W) dianions

et al. 2014

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Herein, we have evaluated relative changes in M–S electronic structure and orbital mixing in Group 6 MS42- dianions using solid- and solution-phase S K-edge X-ray absorption spectroscopy (XAS; M = Mo, W), as well as density functional theory (DFT; M = Cr, Mo, W) and time-dependent density functional theory (TDDFT) calculations. To facilitate comparison with solution measurements (conducted in acetonitrile), theoretical models included gas-phase calculations as well as those that incorporated an acetonitrile dielectric, the latter of which provided better agreement with experiment. Two pre-edge features arising from S 1s → e* and t2* electron excitations were observed in the S K-edge XAS spectra and were reasonably assigned as 1A1 → 1T2 transitions. For MoS42-, both solution-phase pre-edge peak intensities were consistent with results from the solid-state spectra. For WS42-, solution- and solid-state pre-edge peak intensities for transitions involving e* were equivalent, while transitions involving the t2* orbitals were less intense in solution. Experimental and computational results have been presented in comparison to recent analyses of MO42- dianions, which allowed M–S and M–O orbital mixing to be evaluated as the principle quantum number (n) for the metal valence d orbitals increased (3d, 4d, 5d). Overall, the M–E (E = O, S) analyses revealed distinct trends in orbital mixing. For example, as the Group 6 triad was descended, e* (π*) orbital mixing remained constant in the M–S bonds, but increased appreciably for M–O interactions. For the t2* orbitals (σ* + π*), mixing decreased slightly for M–S bonding and increased only slightly for the M–O interactions. These results suggested that the metal and ligand valence orbital energies and radial extensions delicately influenced the orbital compositions for isoelectronic ME42- (E = O, S) dianions.

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Carbon K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory Examination of Metal–Carbon Bonding in Metallocene Dichlorides

Cited by 48 publications

References 90 publications

Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl₂ Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl₂ Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

Synthesis and characterization of a new and electronically unusual uranium metallacyclocumulene, (C5Me5)2U(η4-1,2,3,4-PhC4Ph)

Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M–S bonding for MS₄²⁻(M = Cr, Mo, W) dianions

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Carbon K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory Examination of Metal–Carbon Bonding in Metallocene Dichlorides

Cited by 48 publications

References 90 publications

Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl2 Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl2 Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

Synthesis and characterization of a new and electronically unusual uranium metallacyclocumulene, (C5Me5)2U(η4-1,2,3,4-PhC4Ph)

Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M–S bonding for MS42−(M = Cr, Mo, W) dianions

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Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl₂ Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

Solution and Solid‐State Ligand K‐Edge XAS Studies of PdCl₂ Diphosphine Complexes with Phenyl and Cyclohexyl Substituents

Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M–S bonding for MS₄²⁻(M = Cr, Mo, W) dianions