Organometallics
ARTICLE
presence of both menthyl species. The sample was then divided into two
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1
chloride (Aldrich) or (þ)-neomenthyl chloride; the H NMR spectra
confirmed the identification of the decomposition products.33 GC
analysis was also carried out on a Shimadzu QP2010 Plus GC-MS with
a SHRX1-5MS column; the injection temperature was 280 °C, and the
initial column temperature was 50 °C. After a 2 min lag time, the column
was heated from 50 to 280 °C at a rate of 20 °C/min. The end
temperature was then held for 3 min. The retention times for pure
samples of (-)-menthyl chloride, (þ)-neomenthyl chloride, and the
experimental sample were identical (8.25 min).
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Similarly, an NMR tube containing a solution of Pt(dppe)(Men)(Br)
(2, 10 mg) in 1 mL of CDCl3 was sealed with Parafilm and kept at room
temperature in the light. 31P NMR after 7 days revealed complete
degradation of the sample to a mixture of Pt(dppe)Cl2, Pt(dppe)(Cl)-
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(12) Some literature procedures for preparation of menthyl
Grignard reagents, including the one we used (Vedejs, E.; Donde, Y. J.
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dibromoethane to activate the magnesium. The presence of bromide
may affect the structure and reactivity of the reagent. For comparison,
experimental procedures in refs 16b, 16c include dibromoethane, while
EtBr was used in Tanaka, M.; Ogata, I. Bull. Chem. Soc. Jpn. 1975,
48, 1094 and others do not mention any additives (Dakternieks, D.;
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1
(Br), and Pt(dppe)Br2.27 The H NMR spectrum showed two major
menthene species, trans-2-menthene and 3-menthene, with diagnostic
peaks at 5.53 ppm (br s, 2H) and 5.36 ppm (br s, 1H), respectively.34
This decomposition was unaffected when the sample was kept in the
dark, or when CDCl3 that had been passed over basic alumina was used.
To confirm the identities of the menthenes, the NMR sample containing
the degradation products was divided into two aliquots, which were then
treated with authentic samples of either trans-2-menthene (Aldrich) or
3-menthene.41
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’ ASSOCIATED CONTENT
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S
Supporting Information. Crystallographic details, in-
b
cluding CIF files, and NMR spectra. This material is available free
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’ AUTHOR INFORMATION
Corresponding Author
*E-mail: Glueck@Dartmouth.Edu.
’ ACKNOWLEDGMENT
We thank the NSF for support and Dartmouth College for
Zabriskie Fellowships to A.Z.
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(25) (a) The related cyclohexyl complex Pt(dcpe)(Cy)(Cl) (dcpe =
Cy2PCH2CH2PCy2, Cy = cyclohexyl) was also reported to decompose
in solution and could not be isolated in pure form: Hackett, M.;
1816
dx.doi.org/10.1021/om1008555 |Organometallics 2011, 30, 1812–1817