Variation in crystallization conditions allows the isolation of trimeric as well as dimeric and monomeric forms of [(alkyl isocyanide)4RhI]+

Tran, Ngon T.; Stork, Jay R.; Pham, David M.; Olmstead, Marilyn M.; Fettinger, James C.; Balch, Alan L.

doi:10.1039/b513700d

Cited by 25 publications

(41 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Balch and coworkers specifically discuss the symmetry-conditioned interplay of p z -d z2 bonding in dimeric and trimeric [Rh(alkylisocyanide) 4 ] + . [32] We also found support for the p z -d z2 interaction in a natural bond orbital (NBO) 2 nd order perturbation theory analysis. [41] A substantial contribution (E(2) = -75 kcal/mol) is obtained for just this interaction.…”

Section: Energetics Of Oligomerization and The Reasons For Itsupporting

confidence: 54%

“…In the dimers and trimers of the related [Rh(alkylisocyanide) 4 ] + there is a different outcome, as far as distances are concerned. [32] There is good evidence for aggregation of d 8 dimers in solution, [33,34] so the general effecta substantial driving force for aggregationwas anticipated. But the magnitude of the energetics involved came as a bit of a surprise to us .…”

Section: Energetics Of Oligomerization and The Reasons For Itmentioning

confidence: 99%

See 1 more Smart Citation

Revisiting Ir(CO)3Cl

2016

View full text Add to dashboard Cite

We return to an old puzzlethe short metal-metal separation and electrical conductivity of the apparently unoxidized one-dimensionally stacked structure of a d 8 Ir(I) complex, Ir(CO) 3 Cl. One would expect neither a short Ir-Ir distance of 2.84 Å, nor metallicity in an unoxidized stacked square-planar d 8 array. We build up dimer, trimer, one-dimensional polymer and model 3-dimensional structures, in both molecular and extended structure plane wave calculations. The short Ir-Ir separation in the polymer, with a substantial contribution of 6p z -5d z2 bonding to it, is obtained without any oxidation. There is computational evidence for an important level crossing in the polymer. The metallicity remains unexplained, but likely arises from partial oxidation. And that remains an outstanding experimental issue. ] G. A. Landrum, YAeHMOP: Yet Another extended Hückel Molecular Orbital Package, Version 3.0; http://sourceforge.net/projects/yaehmop/. *Graphical Abstract -Pictogram (for review)One would expect neither a short Ir-Ir distance of 2.84 Å, nor metallicity in an unoxidized stacked square-planar d 8 array, as one sees in the structure of Ir(CO) 3 Cl. In calculations, a short Ir-Ir separation is obtained and explained, without any oxidation. The metallicity remains a puzzle. *Graphical Abstract -Synopsis (for review)

show abstract

Section: Energetics Of Oligomerization and The Reasons For Itsupporting

confidence: 54%

Section: Energetics Of Oligomerization and The Reasons For Itmentioning

confidence: 99%

Revisiting Ir(CO)3Cl

2016

View full text Add to dashboard Cite

show abstract

“…Data for eight (meta) generalized gradient approximation DFAs, abbreviated as (m)GGA, (namely BLYP 7(b) with its corresponding dispersion corrected values). This and related complexes have been studied intensively and the property of oligomer formation in solution has been an "open case" for many years [121][122][123] . Quantum chemical calculations have been able to assign the main binding motif of this highly charged system to be the London dispersion thus making it an ideal test case for the DFT-D4 method.…”

Section: B Non-covalent Interactions and Conformational Energiesmentioning

confidence: 99%

A Generally Applicable Atomic-Charge Dependent London Dispersion Correction Scheme

Caldeweyher

Ehlert²,

Hansen³

et al. 2019

Preprint

View full text Add to dashboard Cite

The D4 model is presented for the accurate computation of London dispersion interactions in density functional theory approximations (DFT-D4) and generally for atomistic modeling methods. In this successor to the DFT-D3 model, the atomic coordination-dependent dipole polarizabilities are scaled based on atomic partial charges which can be taken from various sources. For this purpose, a new charge-dependent parameter-economic scaling function is designed. Classical charges are obtained from an atomic electronegativity equilibration procedure for which efficient analytical derivatives are developed. A numerical Casimir-Polder integration of the atom-in-molecule dynamic polarizabilities yields charge- and geometry-dependent dipole-dipole dispersion coefficients. Similar to the D3 model, the dynamic polarizabilities are pre-computed by time-dependent DFT and elements up to radon are covered. For a benchmark set of 1225 dispersion coefficients, the D4 model achieves an unprecedented accuracy with a mean relative deviation of 3.8% compared to 4.7% for D3. In addition to the two-body part, three-body effects are described by an Axilrod-Teller-Muto term. A common many-body dispersion expansion was extensively tested and an energy correction based on D4 polarizabilities is found to be advantageous for some larger systems. Becke-Johnson-type damping parameters for DFT-D4 are determined for more than 60 common functionals. For various energy benchmark sets DFT-D4 slightly outperforms DFT-D3. Especially for metal containing systems, the introduced charge dependence improves thermochemical properties. We suggest (DFT-)D4 as a physically improved and more sophisticated dispersion model in place of DFT-D3 for DFT calculations as well as for other low-cost approaches like semi-empirical models.<br><br>

show abstract

“…Rh I -isocyanide complexes were reported to display short unsupported Rh I -Rh I (∼3.1 Å) distances in the X-ray crystal structures (9,60). EDA calculations are performed on two Rh I atoms in the [Rh-1] 2 dimer at the calculation level of ZORA-B3LYP-D4 (61)/TZ2P (Fig.…”

mentioning

confidence: 99%

Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d⁸and d¹⁰organometallic complexes

Wan

Yang

et al. 2020

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

Metallophilicity is defined as the interaction among closed-shell metal centers, the origin of which remains controversial, particularly for the roles of spd orbital hybridization (mixing of the spd atomic orbitals of the metal atom in the molecular orbitals of metal complex) and the relativistic effect. Our studies reveal that at close M–M′ distances in the X-ray crystal structures of d8 and d10 organometallic complexes, M–M′ closed-shell interactions are repulsive in nature due to strong M–M′ Pauli repulsion. The relativistic effect facilitates (n + 1)s-nd and (n + 1)p-nd orbital hybridization of the metal atom, where (n + 1)s-nd hybridization induces strong M–M′ Pauli repulsion and repulsive M–M′ orbital interaction, and (n + 1)p-nd hybridization suppresses M–M′ Pauli repulsion. This model is validated by both DFT (density functional theory) and high-level coupled-cluster singles and doubles with perturbative triples computations and is used to account for the fact that the intermolecular or intramolecular Ag–Ag′ distance is shorter than the Au–Au′ distance, where a weaker Ag–Ag′ Pauli repulsion plays an important role. The experimental studies verify the importance of ligands in intermolecular interactions. Although the M–M′ interaction is repulsive in nature, the linear coordination geometry of the d10 metal complex suppresses the L–L′ (ligand–ligand) Pauli repulsion while retaining the strength of the attractive L–L′ dispersion, leading to a close unsupported M–M′ distance that is shorter than the sum of the van der Waals radius (rvdw) of the metal atoms.

show abstract

Variation in crystallization conditions allows the isolation of trimeric as well as dimeric and monomeric forms of [(alkyl isocyanide)4RhI]+

Abstract: Trimeric green [(i-PrNC)12Rh(I)3]Cl3.4.5H2O, monomeric [(C6H11NC)4Rh(I)](BPh4) and [(i-PrNC)4Rh(I)](BPh4) (both yellow), and red, dimeric [(C6H11NC)8Rh(I)2]Cl2.0.5C6H6.2H2O have been crystallized.

Cited by 25 publications

References 10 publications

Revisiting Ir(CO)3Cl

Revisiting Ir(CO)3Cl

A Generally Applicable Atomic-Charge Dependent London Dispersion Correction Scheme

Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d⁸and d¹⁰organometallic complexes

Contact Info

Product

Resources

About

Variation in crystallization conditions allows the isolation of trimeric as well as dimeric and monomeric forms of [(alkyl isocyanide)4RhI]+

Abstract: Trimeric green [(i-PrNC)12Rh(I)3]Cl3.4.5H2O, monomeric [(C6H11NC)4Rh(I)](BPh4) and [(i-PrNC)4Rh(I)](BPh4) (both yellow), and red, dimeric [(C6H11NC)8Rh(I)2]Cl2.0.5C6H6.2H2O have been crystallized.

Cited by 25 publications

References 10 publications

Revisiting Ir(CO)3Cl

Revisiting Ir(CO)3Cl

A Generally Applicable Atomic-Charge Dependent London Dispersion Correction Scheme

Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d8and d10organometallic complexes

Contact Info

Product

Resources

About

Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d⁸and d¹⁰organometallic complexes