Electronic properties of n-heterocyclic carbene (NHC) ligands: Synthetic, structural, and spectroscopic studies of (NHC)Platinum(II) complexes

Serena Fantasia, Jeffrey L. Petersen, Heiko Jacobsen, Luigi Cavallo, Steven Patrick Nolan

Research output: Contribution to journalArticlepeer-review

180 Citations (Scopus)

Abstract

N-Heterocyclic carbene complexes of platinum(II) have been synthesized, notably monocarbene complexes cis-[(IPr)Pt(dmso)(Cl)(2)], 6, cis-[(IMes)Pt(dmso)(Cl)(2)], 7, cis- [(SIPr)Pt(dmso)(Cl)(2)], 8, cis[(SIMes)Pt(dmso)(Cl)(2)], 9, and cis- [(TTP)Pt(dmso)(Cl)(2)], 10. All complexes have been fully characterized by multinuclear NMR spectroscopy. Complex 7, 9, and 10 have been characterized by X-ray crystallography. The data obtained have allowed for the differentiation between electronic contributions (a and T) present in the Pt-NHC bond. Supported by computational analyses, the percentage of pi back-donation from the metal to the NHC is found to be on the order of 10%. More interestingly, we find that saturated NHC (SIPr and SIMes) are more efficient pi back-acceptors than their unsaturated NHC congeners (IPr and lMes). The synergistic effect between pi back-donation and sigma donation present in the saturated NHC systems results in increased electron density at the platinum center compared to the bonding situation in the unsaturated NHC examples.

Original languageEnglish
Pages (from-to)5880-5889
Number of pages10
JournalOrganometallics
Volume26
Issue number24
DOIs
Publication statusPublished - 19 Nov 2007

Keywords

  • DENSITY-FUNCTIONAL THEORY
  • NMR CHEMICAL-SHIFTS
  • PALLADIUM/IMIDAZOLIUM SALT SYSTEMS
  • ORDER REGULAR APPROXIMATION
  • OLEFIN METATHESIS CATALYSTS
  • NUCLEAR-MAGNETIC-RESONANCE
  • SPIN COUPLING-CONSTANTS
  • C-H ACTIVATION
  • SUZUKI-MIYAURA
  • TRANSFER HYDROGENATION

Fingerprint

Dive into the research topics of 'Electronic properties of n-heterocyclic carbene (NHC) ligands: Synthetic, structural, and spectroscopic studies of (NHC)Platinum(II) complexes'. Together they form a unique fingerprint.

Cite this