NHC Carbene–Metal Complex Ligand Binding Energies

Edwards, Kyle C.; Vasiliu, Monica; Maxwell, Jackson W.; Castillo, Clarisa E.; Marion, Daniel M.; Craciun, Raluca; Hall, James Fletcher; Tapu, Daniela; Dixon, David A.

doi:10.1021/acs.jpca.3c06409

Cited by 2 publications

(3 citation statements)

References 64 publications

(118 reference statements)

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“…The LBEs for the carbenes are noticeably larger than the LBEs for the corresponding complexes with PH 3 . The presence of additional methyl groups in the carbene structure stabilizes the complex and increases the LBEs for carbenes B and D compared to their unsubstituted analogs but not by large amounts …”

Section: Resultsmentioning

confidence: 99%

“…Binding PH 3 or an NHC to M(NH 3 ) 2 group 10 neutrals and group 11 cationic species can displace an NH 3 , which then can bind to the other NH 3 ligand through a hydrogen bond. Such a displacement could happen because PH 3 is a better lone pair (LP) donor or because there is a substantially stronger hydrogen bond between two NH 3 groups.…”

Section: Resultsmentioning

confidence: 99%

“…Although both phosphines and carbenes are σ-donating ligands with the ability to act as π acceptors, there are differences between them that are important in their catalytic behavior as ligands. The goal of the current work is to provide an expanded set of energies of the metal–phosphine bonds and the electron distribution analysis of the metal–phosphine complexes as well as a comparative analysis of the previously obtained results for metal–carbene complexes. , The current work includes binding energies of the groups 1 and 11 monocations, group 2 dications, and group 10 neutral species to PH 3 , PMe 3 , and PPh 3 . The interactions of PPh 3 with the various atomic species have been described in detail …”

Section: Introductionmentioning

confidence: 99%

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Phosphine versus Carbene Metal Interactions: Bond Energies

Duda,

Edwards,

Dixon

2024

Inorg. Chem.

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A variety of different ground-state structures of carbene and phosphine groups 1 and 2 cationic, group 11 cationic, and group 10 neutral complexes were studied using density functional theory (DFT) and correlated molecular orbital theory (CCSD(T)) methods. Geometries of complexes with phosphines were studied and compared to available experimental data. Among the three analyzed phosphine ligands, PH 3 , PMe 3 , and PPh 3 , PH 3 was found to have noticeably smaller ligand binding energies (LBEs, ΔH 298 K ). PPh 3 has the greatest LBEs with group 2 dications. The difference in LBEs for PMe 3 and PPh 3 in complexes with group 1 monocations and transition-metal (TM) complexes was significantly less pronounced. The stability and reactivity of phosphine complexes were analyzed and compared with those of previously studied N-heterocyclic carbenes (NHC). PH 3 has smaller LBEs compared to NHC carbenes. The lower LBEs correlate with the hardness for M(11) + complexes and correlate with both the hardness and ionic radii for the M(1) + and M(2) 2+ complexes. The presence of additional PH 3 substituents on the metal center makes the LBE smaller compared to their unsubstituted or less substituted analogs. The presence of NH 3 in a structure causes a smaller effect on binding, and, except for carbene−PtNH 3 , an increase in LBE was observed. Composite-correlated molecular orbital theory (G3MP2) was used to predict the LBE of various Lewis acidic ligands with PH 3 and NHCs to contrast their binding behavior. Binding either phosphine or carbene to metal diamine complexes caused ligand exchange and transfer of NH 3 to an outer coordination sphere.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%