ic202164v_si_005.cif (26.08 kB)
Rhodium Complexes of a Chelating Ligand with Imidazol-2-ylidene and Pyridin-2-ylidene Donors: The Effect of C-Metalation of Nicotinamide Groups on Uptake of Hydride Ion
dataset
posted on 2012-02-20, 00:00 authored by Alex McSkimming, Graham E. Ball, Mohan M. Bhadbhade, Stephen B. ColbranRhodium complexes of the imidazolylidene (C-im) N-heterocyclic carbene (NHC) ligand, C-im-pyH+, bearing a nicotinamide cation substituent
(pyH+) have been targeted for ligand-centered uptake and
delivery of hydride
ion. This work reveals that rhodium(I) complexes such as [Rh(C-im-pyH+)(COD)X][PF6] (1, a: X = Cl, b: X = I) undergo facile C-metalation of the nicotinamide ring to afford rhodium
complexes of a novel chelate ligand, C,C′-im-py,
with coordinated imidazolylidene (Cim) and pyridylidene
(Cpy) NHC-donors. Seven examples were characterized and
include rhodium(III) monomers of the general formula [Rh(C,C′-im-py)LxI2]z+ (2: z = 1, L = H2O or solvent, x = 2; 3, 5, 7: z = 0, L = carboxylate, x = 1) and novel rhodium(II) dimers, the anti/syn-isomers of [Rh2(C,C′-im-py)2(μOAc)2I2] (4-anti/syn). The
NMR data, backed by DFT calculations, is consistent with attribution
of the C,C′-im-py ligand as a bis(carbene)
donor. Single crystal X-ray diffraction studies are reported for 2, 3, 4-anti, 4-syn and 7. Consistently, within the each complex, the Rh–Cim bond length is shorter than the Rh–Cpy bond length, which is the opposite trend to that expected based
on simple electronic considerations. It is proposed that intramolecular
steric interactions imposed by different rings in the rigid C,C′-im-py chelate ligand dictate the observed Rh–CNHC bond lengths. Attempts to add hydride to the C-metalated nicotinamide ring in 3 were unsuccessful.
The redox behavior of 3 and 4 and, for comparison,
an analogous bis(imidazolylidene)rhodium(III) monomer (8), were characterized by cyclic voltammetry, electron paramagnetic
resonance (EPR), and UV–vis spectroelectrochemistry. In 3 and 4, the C-metalated nicotinamide
ring is found to exhibit a one-electron reduction process at far lower
potential (−2.34 V vs. Fc+/Fc in acetonitrile) than
the two-electron nicotinamide cation-dihydronicotinamide couple found
for the corresponding nonmetalated ring (−1.24 V). The C,C′-ligand is electrochemically silent over a large
potential range (from −2.3 V to the anodic solvent limit),
thus for both 3 and 4 the first reduction
processes are metal-centered. For 4-anti, the cyclic voltammetry and UV–vis spectrochemical
results are consistent with a diamagnetic [Rh(I)Rh(II)]2 tetrameric reduction product. Density functional theory (DFT) calculations
were used to further probe the uptake of hydride ion by the nicotinamide
ring, both before and after C-metalation. It is found
that C-metalation significantly decreases the ability
of the nicotinamide ring to take up hydride ion, which is attributed
to the “carbene-like” character of a C-metalated pyridylidene ring.