Dalton Transactions 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, Recommanded Product: 2,6-Bis((di-tert-butylphosphino)methyl)pyridine.
Lee, Kyounghoon published the artcileLigand K-edge XAS, DFT, and TDDFT analysis of pincer linker variations in Rh(I) PNP complexes: reactivity insights from electronic structure, Recommanded Product: 2,6-Bis((di-tert-butylphosphino)methyl)pyridine, the publication is Dalton Transactions (2016), 45(24), 9774-9785, database is CAplus and MEDLINE.
Here we report P K-edge, Cl K-edge, and Rh L3-edge X-ray absorption spectroscopy (XAS) data for Rh[C5H3N-2,6-(XPtBu2)2]Cl, where X = O (tBuPONOP; 1) or CH2 (tBuPNP; 2), I and II, resp. Solid-state XAS data for 1 and 2 were compared to d. functional theory (DFT) and time-dependent d. functional theory (TDDFT) calculations to identify how changing the PNP pincer linker from O to CH2 affected electronic structure and bonding at Rh(I). Pronounced differences in XAS peak intensities and energies were observed The P K-edge XAS data revealed a large increase in Rh 4dx2-y2 and P 3p orbital-mixing (Rh-P Ï*) in 1 compared to 2, and pronounced transition energy variations reflected marked differences in orbital energies and compositions By comparison, the Cl K-edge XAS data revealed only subtle differences in Rh-Cl covalency, although larger splitting between the Rh-Cl Ï* and Ï* transitions was observed in 2. Anal. of the occupied MOs from DFT (HOMO, HOMO-1, HOMO-2, and HOMO-3) and comparison to the unoccupied MOs involved in XAS revealed a relatively uniform energy increase (ca. 0.3-0.5 eV) for all five 4d-derived MOs in Rh(tBuPNP)Cl (2) compared to Rh(tBuPONOP)Cl (1). The energy shift was relatively invariant with respect to differences in orbital symmetry, bonding type (Ï or Ï), and orbital mixing, which suggested that the increase could be attributed to electrostatic effects. The change in d-orbital energies are consistent with known reactivity differences of Rh(tBuPONOP)+ and Rh(tBuPNP)+ towards CO, H2, and CH2Cl2, and are explained here by considering how d-orbital energies affect covalent L â?M Ï bonding and M â?L Ï backbonding.
Dalton Transactions 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, Recommanded Product: 2,6-Bis((di-tert-butylphosphino)methyl)pyridine.
Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem