Impact of Halide (Cl vs I) Identity on the Preferred Positioning of Substituents between Al and M (M = Co, Rh, Ir) in PAlP Pincer Complexes
Issued Date
2025-01-13
Resource Type
ISSN
02767333
eISSN
15206041
Scopus ID
2-s2.0-85214815891
Journal Title
Organometallics
Volume
44
Issue
1
Start Page
347
End Page
353
Rights Holder(s)
SCOPUS
Bibliographic Citation
Organometallics Vol.44 No.1 (2025) , 347-353
Suggested Citation
Lee S.R., Keawkla N., Sladek R.N., Bhuvanesh N., Surawatanawong P., Ozerov O.V. Impact of Halide (Cl vs I) Identity on the Preferred Positioning of Substituents between Al and M (M = Co, Rh, Ir) in PAlP Pincer Complexes. Organometallics Vol.44 No.1 (2025) , 347-353. 353. doi:10.1021/acs.organomet.4c00490 Retrieved from: https://repository.li.mahidol.ac.th/handle/20.500.14594/102823
Title
Impact of Halide (Cl vs I) Identity on the Preferred Positioning of Substituents between Al and M (M = Co, Rh, Ir) in PAlP Pincer Complexes
Author's Affiliation
Corresponding Author(s)
Other Contributor(s)
Abstract
Protolysis of AlMe3 or AlEt3 with 2-diisopropylphosphinopyrrole (1) resulted in alane/bis(phosphine) pincer ligands containing two flanking phosphines and a central Al-Me (2-Me), Al-Et (2-Et) unit. Reactions of 2-Me with [(COD)MI]2 (COD = 1,5-cyclooctadiene; M = Rh or Ir) in the presence of pyridine produced pincer complexes (3-Rh-I and 3-Ir-I) with M supported by the PAlP tridentate ligand, and pyridine, methyl, and iodide as monodentate ligands for Al or M. The analogous reaction of 2-Et with [(COD)MI]2 and pyridine resulted in the formation of the analogous compounds 4-Rh-I and 4-Ir-I with hydride in place of methyl. DFT calculations were used to analyze the thermodynamic preferences for the positioning of pyridine, methyl or hydride, and the halide (chloride or iodide) on M vs Al. Cobalt was included with Rh and Ir among M for the purposes of DFT calculations. Theoretical studies suggested that different isomers are preferred for the iodide complexes (M-I and Al-Py) than for the chloride ones (M-py and Al-Cl, previously reported for Rh and Ir). X-ray structural study of 3-Rh-I and analysis of the 1H NMR data of the Rh and Ir compounds in benzene corroborated these predictions.