"Long-range" metal-ligand cooperation in H2 activation and ammonia-promoted hydride transfer with a ruthenium-acridine pincer complex.

@article{Gunanathan2010LongrangeMC,
  title={"Long-range" metal-ligand cooperation in H2 activation and ammonia-promoted hydride transfer with a ruthenium-acridine pincer complex.},
  author={Chidambaram Gunanathan and Boopathy Gnanaprakasam and Mark A. Iron and Linda J. W. Shimon and David Milstein},
  journal={Journal of the American Chemical Society},
  year={2010},
  volume={132 42},
  pages={
          14763-5
        }
}
The acridine-based pincer complex 1 exhibits an unprecedented mode of metal-ligand cooperation involving a "long-range" interaction between the distal acridine C9 position and the metal center. Reaction of 1 with H(2)/KOH results in H(2) splitting between the Ru center and C9 with concomitant dearomatization of the acridine moiety. DFT calculations show that this process involves the formation of a Ru dihydride intermediate bearing a bent acridine ligand in which C9 is in close proximity to a… 
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A new mode of activation of CO2 by metal-ligand cooperation with reversible C-C and M-O bond formation at ambient temperature.
TLDR
A new mode of metal-ligand cooperative activation of CO(2) to a ruthenium PNP pincer complex involving aromatization/dearomatization steps is presented in experimental and theoretical studies.
Activation of nitriles by metal ligand cooperation. Reversible formation of ketimido- and enamido-rhenium PNP pincer complexes and relevance to catalytic design.
TLDR
The reversible binding of the nitrile in the enamido compound cis-[Re(PNP(tBu)-HNC═CHPh)(CO)2] (9) was demonstrated via the displacement of benzyl cyanide from 9 by CO.
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The role of pendant boron ligands in ammonia–borane (AB) dehydrogenation has been investigated using hybrid density functional theory for two very efficient ruthenium-based catalysts developed by…
Alcohol amination with ammonia catalyzed by an acridine-based ruthenium pincer complex: a mechanistic study.
TLDR
The detailed analysis of a series of possible catalytic pathways leads to the conclusion that the most favorable pathway for this catalyst does not require metal-ligand cooperation.
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TLDR
It is demonstrated that hemilability of homofunctionalized ligands can be affected by careful adjustment of geometric parameters.
Bottom-Up Construction of a CO2-Based Cycle for the Photocarbonylation of Benzene, Promoted by a Rhodium(I) Pincer Complex.
TLDR
Rhodium-Hydride PNP pincer complex 1 is shown to add CO2 in two disparate pathways: one is the expected insertion of CO2 into the metal-hydride bond, and the other leads to reductive cleavage ofCO2, involving metal-ligand cooperation.
Synthesis, Coordination Chemistry, and Cooperative Activation of H2 with Ruthenium Complexes of Proton‐Responsive METAMORPhos Ligands
The synthetic scope of proton-responsive sulfonamidophosphorus (METAMORPhos) ligands is expanded and design principles for the selective formation of particular tautomers, ion pairs, or double…
Metal–Ligand Cooperation as Key in Formation of Dearomatized NiII–H Pincer Complexes and in Their Reactivity toward CO and CO2
TLDR
The unique synthesis and reactivity of [(RPNP*)NiH] complexes (1a,b), based on metal–ligand cooperation (MLC), are presented and have been fully characterized by NMR and X-ray crystallography.
Bond activation and catalysis by ruthenium pincer complexes.
TLDR
The heterolytic activation of dihydrogen by NH/H2 MLC was reported by Fryzuk and co-workers in 1987 with pincer Ir and Rh complexes, and complex 73 was found to be an active dehydrogenation catalyst for ammoniaborane and hydrogenation reactions as discussed below.
Anionic nickel(II) complexes with doubly deprotonated PNP pincer-type ligands and their reactivity toward CO2
The aromatization–dearomatization reaction of pincer-type complexes prompted by protonation–deprotonation of the pincer “arm” is a key step in bond activation chemistry and atom-economic catalytic…
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