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

doi:10.1021/om700857j

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 journal › Article › peer-review

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 language	English
Pages (from-to)	5880-5889
Number of pages	10
Journal	Organometallics
Volume	26
Issue number	24
DOIs	https://doi.org/10.1021/om700857j
Publication status	Published - 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

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@article{7aeedffee9b54d10a3ffcbb679e32f9b,

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

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",

author = "Serena Fantasia and Petersen, {Jeffrey L.} and Heiko Jacobsen and Luigi Cavallo and Nolan, {Steven Patrick}",

year = "2007",

month = nov,

day = "19",

doi = "10.1021/om700857j",

language = "English",

volume = "26",

pages = "5880--5889",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society (ACS)",

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TY - JOUR

T1 - Electronic properties of n-heterocyclic carbene (NHC) ligands: Synthetic, structural, and spectroscopic studies of (NHC)Platinum(II) complexes

AU - Fantasia, Serena

AU - Petersen, Jeffrey L.

AU - Jacobsen, Heiko

AU - Cavallo, Luigi

AU - Nolan, Steven Patrick

PY - 2007/11/19

Y1 - 2007/11/19

N2 - 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.

AB - 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.

KW - DENSITY-FUNCTIONAL THEORY

KW - NMR CHEMICAL-SHIFTS

KW - PALLADIUM/IMIDAZOLIUM SALT SYSTEMS

KW - ORDER REGULAR APPROXIMATION

KW - OLEFIN METATHESIS CATALYSTS

KW - NUCLEAR-MAGNETIC-RESONANCE

KW - SPIN COUPLING-CONSTANTS

KW - C-H ACTIVATION

KW - SUZUKI-MIYAURA

KW - TRANSFER HYDROGENATION

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U2 - 10.1021/om700857j

DO - 10.1021/om700857j

M3 - Article

SN - 0276-7333

VL - 26

SP - 5880

EP - 5889

JO - Organometallics

JF - Organometallics

IS - 24

ER -

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

Abstract

Keywords

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