(Ar-C), 127.10 (Ar-C), 128.24 (Ar-C), 129.00 (Ar-C), 129.65 (Ar-
C), 130.23 (Ar-C), 130.43 (Ar-C), 130.90 (br, Ar-C), 131.52 (t,
2JPC = 5.03 Hz, o-Ar-C), 132.25 (br, Ar-C), 138.74 (Ar-C), 150.74
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1
(Ar-C) and 152.69 (d, 2JPC = 2.01 Hz, ipso-Ar-C). 31P{ H} NMR
1
(d6-benzene, 298 K): d 6.30 (d, 2JYP = 12.96 Hz, NPC). 29Si{ H}
NMR (d6-benzene, 298 K): d -9.14 (s, NSi(CH3)3). IR v/cm-1
(Nujol): 1592 (br, m), 1261 (s), 1093 (s), 1020 (s), 800 (s).
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Crystal data for compounds 2–6 are given in Table 2, and
further details of the structure determinations are in the ESI.†
Bond lengths and angles are listed in Table 1. Crystals were
examined on a Bruker AXS CCD area detector diffractometer
˚
using graphite-monochromated Mo Ka radiation (l = 0.71073 A).
12 M. Zimmermann, J. Takats, G. Kiel, K. W. To¨rnoos and R. Anwander,
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Intensities were integrated from a sphere of data recorded on
narrow (0.3◦) frames by w rotation. Cell parameters were refined
from the observed positions of all strong reflections in each data
set. Semi-empirical absorption corrections were applied, based
on symmetry-equivalent and repeat reflections. The structures
were solved by direct methods and were refined by least-squares
methods on all unique F2 values, with anisotropic displacement
parameters, and with constrained riding hydrogen geometries;
U(H) was set at 1.2 (1.5 for methyl groups) times Ueq of the parent
atom. The largest features in final difference syntheses were close
to heavy atoms. The Flack parameter for 2 refined to 0.007(4).
Highly disordered solvent molecules of crystallisation in 4 and 5
could not be modelled and were treated with the Platon SQUEEZE
procedure.34 Programs were Bruker AXS SMART (control) and
SAINT (integration),35 and SHELXTL for structure solution,
refinement, and molecular graphics.36
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Density functional theory calculations
The calculations were performed using the Amsterdam Density
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tivistic geometry optimization DFT calculations for 3 employed a
Slater type orbital (STO) triple-z-plus one polarization function
basis set from the ZORA/TZP database of the ADF suite for all
atoms. Frozen core basis sets were used for C (1 s), N (1 s), O (1 s),
Si (2p), P (2p) and Y (4p). Scalar relativistic (SR) approaches
were used within the ZORA Hamiltonian for the inclusion of
relativistic effects. The local density approximation (LDA) with
the correlation potential due to Vosko et al was used in all of the
DFT calculations.39 Gradient corrections were performed using
the functionals of Becke40 and Perdew41 (BP). The Kohn–Sham
orbitals were visualized in MOLEKEL.42
23 S. Harder, C. Ruspic, N. N. Bhriain, F. Berkermann and M. Schu¨rmann,
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25 M. Schlosser and J. Hartmann, Angew. Chem., Int. Ed. Engl., 1973, 12,
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Acknowledgements
We thank the Royal Society, the EPSRC, the NSCCS, and the
University of Nottingham for supporting this work.
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4554 | Dalton Trans., 2009, 4547–4555
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