(
)
I.L. Eremenko et al.rJournal of Organometallic Chemistry 551 1998 171–194
193
3.1.7. Crystal structure determinations
The crystals were all mounted in air on glass fibers using 5 min epoxy resin. The unit cells were determined and
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.
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refined from 24 equivalent reflections with 2Q)22–288 and obtained from Syntex P21 for II , CAD-4 for VII–IX ,
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.
and Siemens R3vrm for IV, V, and N-phenyl-o-phenylenediamine four-circle diffractometers at room temperature.
Intensity data sets were corrected for the Lorentz and polarization effects. Backgrounds were scanned for 25 of the
peak widths on each end of the scan. Three reflections were monitored periodically for each compound as a check for
crystal decomposition or movement. No significant variation in these standards was observed, so no correction was
applied. Details of crystal parameters, data collection and structure refinement are given in Table 8.
All structures were solved by a direct method to locate the platinum or palladium atoms for II, IV, V, VII, and
VIII. For IX at this stage, all nonhydrogen atoms were found. The other atoms in II, IV, V, VII, and VIII were located
w
x
in the subsequent difference Fourier maps. The DIFABS method 27 was used for the absorption correction of IV, V,
VII, and VIII at the stage of the isotropic approximation. An anisotropic refinement was applied to all nonhydrogen
atoms, and all hydrogen atoms in the structures were found from the difference Fourier maps and refined in the
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isotropic approximation for, IV, V, VII, VIII and the initial ligand . For II, the H atoms were included in calculations
2
˚
as fixed contributions with the constant isotropic temperature factor uiso s0.08 A . The computations were performed
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x
using the SHELXTL PLUS program package 28 on a Pentium 100r16 computer. Selected bond lengths and angles
for investigated complexes are given in Tables 1–7 and the positional parameters and the equivalent thermal
parameters are listed in Tables 9–15. Complete lists of the bond lengths and angles and the tables of thermal
parameters have been deposited at the Cambridge Crystallographic Data Centre.
4. Conclusion
The results obtained in this work demonstrated that nitrene ligands can be involved into the chemistry of palladium
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.
and platinum. Unlike some other VIII group metals e.g., Fe, Co, Ru, Os , these elements normally form the more
labile nitrene complexes, which can further react by inserting the nitrene ligand to the C–H bond of an arene molecule
to produce observable products like complex II or polyheterocyclic compound IX. Nevertheless, the data available
seem to be encouraging to the search for the stable nitrene complexes of platinum group metals.
Acknowledgements
We are grateful to T.V. Chernysheva for help in the experiments, N.A. Minaeva for providing the IR spectra, and
S.G. Sakharov for assistance with the NMR spectra. We are also thankful to the Russian Foundation for Basic
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Research Projects No. 96-15-96994, 96-03-33581, and 96-03-34389 for financial support.
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Eremenko
