In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2019, No. 10 ( 2019-03-14), p. 1389-1397
Abstract:
The coordination of pyridine (Py) and benzonitrile (PhCN) to benzene based pincer hydridochlorides [(PCP)IrH(Cl)] ( 1 ), [(POCOP)IrH(Cl)] ( 2 ), [{EtO(O)C‐POCOP}IrH(Cl)] ( 3 ), and [(PCN)IrH(Cl)] ( 4 ) was studied spectroscopically and computationally to deduce the ligand influence. The variable temperature NMR ( 1 H, 31 P, 15 N) and UV/Visible spectroscopic measurements revealed preferential coordination of these N‐donor ligands in the apical position of 1 – 4 and gave the formation enthalpies for the hexacoordinate complexes, which follow the order: 1 ≈ 4 〉 3 〉 2 . This order nicely agrees with the order of Lewis acidity obtained for these complexes in DFT calculations. The orbital and electron density distribution analysis were performed at the DFT/M06 theory level for 1 – 4 and a series of p ‐substituted PCP‐based hydridochlorides. The increasing Lewis acidity of iridium [as a maximum energy, V S,max , of molecular electrostatic potential (MEP)] correlates with decreasing basicity of Cl‐ligand (as MEP minimum, V S,min ) as well as with Hammett σ p parameters of p ‐substituents. Importantly, these properties are conserved upon conversion into the corresponding dihydrides, as shown on the example of 1 and 4 .
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2019.10
DOI:
10.1002/ejic.201801341
Language:
English
Publisher:
Wiley
Publication Date:
2019
detail.hit.zdb_id:
1475009-0
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