CO-induced methyl migration in a rhodium thiophosphoryl pincer complex and its comparison with phosphine-based complexes

The divergent effects of S and P donor ligands

Michael Montag, Irena Efremenko, Gregory Leitus, Yehoshoa Ben-David, Jan M L Martin, David Milstein

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

A cationic Rh(III) aryl-methyl complex, bearing a thiophosphoryl-based SCS-type pincer ligand, undergoes facile migratory insertion upon addition of CO, thereby affording a Rh(III) aryl-acetyl complex. This reactivity diverges from that of structurally analogous Rh(III) aryl-methyl complexes of phosphine-based PCP- and PCN-type pincer ligands, which have been previously shown to undergo C-C reductive elimination upon addition of CO, thereby giving C-C agostic Rh(I) complexes. A comparative DFT study of CO migratory insertion in the SCS and PCP complexes reveals that the difference in reactivity originates from the higher electrophilicity of the sulfur atoms of the SCS ligand relative to the phosphorus atoms of the PCP ligand. This leads to decreased Rh → CO π back-donation in the SCS system, resulting in CO labilization and facilitating the metal-to-CO methyl migration. In the PCP system it leads to stronger Rh-CO bonding, which enhances OC → Rh → arene σ donation, thereby weakening the Rh-Cipso bond and facilitating metal-to-Cipso methyl migration.

Original languageEnglish
Pages (from-to)7163-7180
Number of pages18
JournalOrganometallics
Volume32
Issue number23
DOIs
Publication statusPublished - Dec 9 2013

Fingerprint

phosphine
Rhodium
Carbon Monoxide
rhodium
phosphines
Ligands
ligands
insertion
reactivity
metals
Bearings (structural)
atoms
phosphorus
Metals
Pregnenolone Carbonitrile
elimination
sulfur
Atoms
Sulfur
Discrete Fourier transforms

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

CO-induced methyl migration in a rhodium thiophosphoryl pincer complex and its comparison with phosphine-based complexes : The divergent effects of S and P donor ligands. / Montag, Michael; Efremenko, Irena; Leitus, Gregory; Ben-David, Yehoshoa; Martin, Jan M L; Milstein, David.

In: Organometallics, Vol. 32, No. 23, 09.12.2013, p. 7163-7180.

Research output: Contribution to journalArticle

Montag, Michael ; Efremenko, Irena ; Leitus, Gregory ; Ben-David, Yehoshoa ; Martin, Jan M L ; Milstein, David. / CO-induced methyl migration in a rhodium thiophosphoryl pincer complex and its comparison with phosphine-based complexes : The divergent effects of S and P donor ligands. In: Organometallics. 2013 ; Vol. 32, No. 23. pp. 7163-7180.
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