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Electronic properties of N-heterocyclic carbene (NHC) ligands : synthetic, structural, and spectroscopic studies of (NHC)platinum(II) complexes

(2007) ORGANOMETALLICS. 26(24). p.5880-5889
Author
Organization
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.
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

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MLA
Fantasia, Serena, et al. “Electronic Properties of N-Heterocyclic Carbene (NHC) Ligands : Synthetic, Structural, and Spectroscopic Studies of (NHC)Platinum(II) Complexes.” ORGANOMETALLICS, vol. 26, no. 24, 2007, pp. 5880–89.
APA
Fantasia, S., Petersen, J. L., Jacobsen, H., Cavallo, L., & Nolan, S. (2007). Electronic properties of N-heterocyclic carbene (NHC) ligands : synthetic, structural, and spectroscopic studies of (NHC)platinum(II) complexes. ORGANOMETALLICS, 26(24), 5880–5889.
Chicago author-date
Fantasia, Serena, Jeffrey L Petersen, Heiko Jacobsen, Luigi Cavallo, and Steven Nolan. 2007. “Electronic Properties of N-Heterocyclic Carbene (NHC) Ligands : Synthetic, Structural, and Spectroscopic Studies of (NHC)Platinum(II) Complexes.” ORGANOMETALLICS 26 (24): 5880–89.
Chicago author-date (all authors)
Fantasia, Serena, Jeffrey L Petersen, Heiko Jacobsen, Luigi Cavallo, and Steven Nolan. 2007. “Electronic Properties of N-Heterocyclic Carbene (NHC) Ligands : Synthetic, Structural, and Spectroscopic Studies of (NHC)Platinum(II) Complexes.” ORGANOMETALLICS 26 (24): 5880–5889.
Vancouver
1.
Fantasia S, Petersen JL, Jacobsen H, Cavallo L, Nolan S. Electronic properties of N-heterocyclic carbene (NHC) ligands : synthetic, structural, and spectroscopic studies of (NHC)platinum(II) complexes. ORGANOMETALLICS. 2007;26(24):5880–9.
IEEE
[1]
S. Fantasia, J. L. Petersen, H. Jacobsen, L. Cavallo, and S. Nolan, “Electronic properties of N-heterocyclic carbene (NHC) ligands : synthetic, structural, and spectroscopic studies of (NHC)platinum(II) complexes,” ORGANOMETALLICS, vol. 26, no. 24, pp. 5880–5889, 2007.
@article{8169771,
  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.},
  author       = {Fantasia, Serena and Petersen, Jeffrey L and Jacobsen, Heiko and Cavallo, Luigi and Nolan, Steven},
  issn         = {0276-7333},
  journal      = {ORGANOMETALLICS},
  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},
  language     = {eng},
  number       = {24},
  pages        = {5880--5889},
  title        = {Electronic properties of N-heterocyclic carbene (NHC) ligands : synthetic, structural, and spectroscopic studies of (NHC)platinum(II) complexes},
  url          = {http://dx.doi.org/10.1021/om700857j},
  volume       = {26},
  year         = {2007},
}

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