Redox, transmetalation, and stacking properties of tetrathiafulvalene-2,3,6,7-tetrathiolate bridged tin, nickel, and palladium compounds

Xie, Jiaze; Boyn, Jan-Niklas; Filatov, Alexander S.; McNeece, Andrew J.; Mazziotti, David A.; Anderson, John S.

doi:10.1039/c9sc04381k

Cited by 35 publications

(75 citation statements)

References 130 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The v2RDM method has been employed extensively as a polynomially scaling replacement for the configuration interaction solver in CASSCF theory [19,[37][38][39][40][41][42]. The computation of the 2-RDM in the dual v2RDM method, presented here, is crucial for its implementation as a solver in the CASSCF theory because at each iteration CASSCF uses the 2-RDM of the active space to perform the self-consistent-field orbital optimization.…”

Section: Discussionmentioning

confidence: 99%

“…The 2-RDM method exploits the pairwise nature of the electron-electron interaction in the electronic Hamiltonian. Variational calculation of the 2-RDM has been applied to the accurate computation of a range of strongly correlated phenomena including polyradical character in conjugated polyaromatic hydrocarbons [19], non-innocent ligand effects in transition-metal complexes [37,38], entanglement-driven non-superexchange mechanisms in bridged transition- * damazz@uchicago.edu metal dimers [39,40], and exciton condensation in molecular-scale electron double layers [41,42].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Dual-cone variational calculation of the two-electron reduced density matrix

Mazziotti

2020

Phys. Rev. A

Self Cite

View full text Add to dashboard Cite

The computation of strongly correlated quantum systems is challenging because of its potentially exponential scaling in the number of electron configurations. Variational calculation of the two-electron reduced density matrix (2-RDM) without the many-electron wave function exploits the pairwise nature of the electronic Coulomb interaction to compute a lower bound on the ground-state energy with polynomial computational scaling. Recently, a dual-cone formulation of the variational 2-RDM calculation was shown to generate the ground-state energy, albeit not the 2-RDM, at a substantially reduced computational cost, especially for higher N -representability conditions such as the T2 constraint. Here we generalize the dual-cone variational 2-RDM method to compute not only the ground-state energy but also the 2-RDM. The central result is that we can compute the 2-RDM from a generalization of the Hellmann-Feynman theorem. Specifically, we prove that in the Lagrangian formulation of the dual-cone optimization the 2-RDM is the Lagrange multiplier. We apply the method to computing the energies and properties of strongly correlated electrons-including atomic charges, electron densities, dipole moments, and orbital occupations-in an illustrative hydrogen chain and the nitrogen-fixation catalyst FeMoco. The dual variational computation of the 2-RDM with T2 or higher N -representability conditions provides a polynomially scaling approach to strongly correlated molecules and materials with significant applications in atomic and molecular and condensed-matter chemistry and physics.

show abstract

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Dual-cone variational calculation of the two-electron reduced density matrix

Mazziotti

2020

Phys. Rev. A

Self Cite

View full text Add to dashboard Cite

show abstract

“…3, that has recently been synthesized and studied. 69 Recent work has considered the effects of different linker molecules between the cobalt centers for tuning the amount of electron correlation for a variety of potential applications. 69 The N/2 (224) natural orbital from Hartree-Fock and variational 2-RDM PASSCF are shown in Fig.…”

Section: Cobalt Complexmentioning

confidence: 99%

Active Space Pair 2-Electron Reduced Density Matrix Theory for Strong Correlation

Head-Marsden,

Mazziotti

2020

Preprint

Self Cite

View full text Add to dashboard Cite

An active space variational calculation of the 2-electron reduced density matrix (2-RDM) is derived and implemented where the active orbitals are correlated within the pair approximation. The pair approximation considers only doubly occupied configurations of the wavefunction which enables the calculation of the 2-RDM at a computational cost of O(r 3 ). Calculations were performed both with the pair active space configuration interaction (PASCI) method and the pair active space self consistent field (PASSCF) method. The latter includes a mixing of the active and inactive orbitals through unitary transformations. The active-space pair 2-RDM method is applied to the nitrogen molecule, the p-benzyne diradical, a newly synthesized BisCobalt complex, and the nitrogenase cofactor FeMoco. The FeMoco molecule is treated in a [120,120] active space. Fractional occupations are recovered in each of these systems, indicating the detection and recovery of strong electron correlation.

show abstract

“…Transmetalation is commonly associated with an organometallic compound and involves a transfer of organic groups or ligands from one metal to another [1][2][3]. It thus provides a common and convenient method for preparing various organo-transition metal complexes, which are otherwise difficult to synthesize via direct metal-ligand self-assembly.…”

Section: Introductionmentioning

confidence: 99%

Zn(II)-to-Cu(II) Transmetalation in an Amide Functionalized Complex and Catalytic Applications in Styrene Oxidation and Nitroaldol Coupling

et al. 2020

View full text Add to dashboard Cite

The mononuclear zinc(II) complex cis-[ZnL2(H2O)2] (1; L = 4-(pyridin-3-ylcarbamoyl)benzoate) was synthesized and characterized. By soaking crystals of 1 in a mixture of DMF-H2O solution containing a slight excess of Cu(NO3)2 × 3H2O a transmetalation reaction occurred affording the related copper(II) complex trans-[CuL2(H2O)2] (2). The structures of the compounds were authenticated by single crystal X-ray diffraction revealing, apart from a change in the isomerism, an alteration in the relative orientation of the chelating carboxylate groups and of the pyridine moieties. H-bond interactions stabilize both geometries and expand them into two-dimensional (2D) networks. The transmetalation was confirmed by SEM–EDS analysis. Moreover, the thermodynamic feasibility of the transmetalation is demonstrated by density-functional theory (DFT) studies. The catalytic activities of 1 and 2 for the oxidation of styrene and for the nitroaldol (Henry) C-C coupling reaction were investigated. The copper(II) compound 2 acts as heterogeneous catalyst for the microwave-assisted oxidation of styrene with aqueous hydrogen peroxide, yielding selectively (>99%) benzaldehyde up to 66% of conversion and with a turnover frequency (TOF) of 132 h−1. The zinc(II) complex 1 is the most active catalyst (up to 87% yield) towards the nitroaldol (Henry) coupling reaction between benzaldehyde and nitro-methane or -ethane to afford the corresponding β-nitro alcohols. The reaction of benzaldehyde with nitroethane in the presence of 1 produced 2-nitro-1-phenylpropanol in the syn and the anti diastereoisomeric forms, with a considerable higher selectivity towards the former (66:34).

show abstract

Redox, transmetalation, and stacking properties of tetrathiafulvalene-2,3,6,7-tetrathiolate bridged tin, nickel, and palladium compounds

Abstract: Capping TTFtt enables facile transmetalation in three different oxidation states.

Cited by 35 publications

References 130 publications

Dual-cone variational calculation of the two-electron reduced density matrix

Dual-cone variational calculation of the two-electron reduced density matrix

Active Space Pair 2-Electron Reduced Density Matrix Theory for Strong Correlation

Zn(II)-to-Cu(II) Transmetalation in an Amide Functionalized Complex and Catalytic Applications in Styrene Oxidation and Nitroaldol Coupling

Contact Info

Product

Resources

About