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 P. Nolan*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

156 Scopus citations

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 (σ and π) present in the Pt-NHC bond. Supported by computational analyses, the percentage of π 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 π back-acceptors than their unsaturated NHC congeners (IPr and IMes). The synergistic effect between π back-donation and σ 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 (US)
Pages (from-to)5880-5889
Number of pages10
JournalOrganometallics
Volume26
Issue number24
DOIs
StatePublished - Nov 19 2007

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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