Gu, Shunyan’s team published research in Organometallics in 39 | CAS: 338800-13-8

Organometallics published new progress about 338800-13-8. 338800-13-8 belongs to pyridine-derivatives, auxiliary class Bis-phosphine Ligands, name is 2,6-Bis((di-tert-butylphosphino)methyl)pyridine, and the molecular formula is C23H43NP2, Safety of 2,6-Bis((di-tert-butylphosphino)methyl)pyridine.

Gu, Shunyan published the artcileUse of Ligand Steric Properties to Control the Thermodynamics and Kinetics of Oxidative Addition and Reductive Elimination with Pincer-Ligated Rh Complexes, Safety of 2,6-Bis((di-tert-butylphosphino)methyl)pyridine, the publication is Organometallics (2020), 39(10), 1917-1933, database is CAplus.

Oxidative addition and reductive elimination reactions are central steps in many catalytic processes, and controlling the energetics of reaction intermediates is key to enabling efficient catalysis. Oxidative addition and reductive elimination reactions using (RPNP)RhX complexes (R = tert-Bu, iso-Pr, mesityl and phenyl; X = Cl, I) were studied to deduce the impact of the size of the phosphine substituents. Using (RPNP)RhCl as starting material, oxidative addition of MeI was observed to produce (RPNP)Rh(Me)(I)Cl, which was followed by reductive elimination of MeCl to form (RPNP)RhI. The thermodn. and kinetics vary with the identity of the substituent R” on P of the PNP ligand. The presence of large steric bulk (e.g., R = tert-Bu, mesityl) on the phosphine favors Rh(I) compared to the presence of two smaller substituents (e.g., R = iso-Pr, phenyl). An Eyring plot for the oxidative addition of MeI to (tBuPNP)RhCl in THF-d8 is consistent with a polar two-step reaction pathway, and the formation of [(tBuPNP)Rh(Me)I]I is also consistent with this mechanism. DFT calculations show steric bulk affects the reaction energies of addition reactions that generate six-coordinate complexes by tens of kcal·mol-1. Ligand steric bulk has a reduced effect (a few kcal·mol-1) on SN2 addition barriers, which only require access to one side of the square plane.

Organometallics published new progress about 338800-13-8. 338800-13-8 belongs to pyridine-derivatives, auxiliary class Bis-phosphine Ligands, name is 2,6-Bis((di-tert-butylphosphino)methyl)pyridine, and the molecular formula is C23H43NP2, Safety of 2,6-Bis((di-tert-butylphosphino)methyl)pyridine.

Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem