Regiospecific C(naphthyl)–H Bond Activation by Platinum(II)
X-ray Crystallography: Crystallographic data and experimental de-
tails for 2a, 2b, 3a, 4a, 5a and 6b are summarized in Table 4. Data
were collected with a Bruker SMART 1000 CCD area-detector dif-
fractometer using graphite monochromated Mo-Kα (λ = 0.71073 Å)
radiation by ω scan. The structures were solved by direct methods
using SHELXS-97[33] and difference Fourier syntheses and refined
with SHELXL-97 incorporated in WinGX 1.64 crystallographic
collective package.[34] All the hydrogen positions for the compound
were initially located in the difference Fourier map, and for the
final refinement, the hydrogen atoms were placed geometrically and
held in the riding mode. The last cycles of refinement included
atomic positions for all the atoms, anisotropic thermal parameters
for all non-hydrogen atoms and isotropic thermal parameters for
all the hydrogen atoms. Full-matrix-least-squares structure refine-
ment against |F2 |. Molecular geometry calculations were per-
formed with PLATON,[35] and molecular graphics were prepared
using ORTEP-3.[36]
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CCDC-823076 (for 2a), -823077 (for 2b), -823078 (for 3a), -823079
(for 4a), -823080 (for 5a) and -823081 (for 6b) contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
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Computational Details: Calculations were performed with the TD-
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kernel, which is the functional derivative of the TD XC potential
with respect to density. We used the local density approximation
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tion of the optical spectra, 70 lowest spin-allowed singlet-singlet
transitions were taken into account. Transition energies and oscil-
lator strengths were interpolated by a Gaussian convolution with
a σ of 0.2 eV. Solvent effects were modelled by the conductor-like
screening model[41] of solvation as implemented in ADF.
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Regioselectivity for subsequent metallation at different C(naphth-
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calculations were performed at the above level of theory for the
cations of the conformers using the ground state optimized struc-
tures. The individual atomic charges (gross charge) calculated by
Mulliken population analysis were used to calculated the con-
densed Fukui functions using ADF.
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Supporting Information (see footnote on the first page of this arti-
cle): ESI-MS spectrum of 5d, description of crystal packing of the
cycloplatinate species and details of TD-DFT calculations
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Acknowledgments
Financial assistance received from the Department of Science and
Technology (DST), Government of India, New Delhi is gratefully
acknowledged.
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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