COMMUNICATIONS
[
6] For a previous experimental study of some labeled n-propanol/Fe
A Novel Hemiporphyrazine Comprising Three
Isoindolediimine and Three Thiadiazole
Units**
complexes, see: S. Karrass, T. Prüsse, K. Eller, H. Schwarz, J. Am.
Chem. Soc. 1989, 111, 9018.
7] The synthesis of the labeled propanols followed well-established
preparative procedures. In brief, the [O-D]propanols were prepared
[
Nagao Kobayashi,* Sayaka Inagaki,
Victor N. Nemykin, and Taro Nonomura
by treatment of the corresponding sodium propanolates with D
The [1,1-D ]-, [2,2-D ]-, [2,2,3,3,3-D ]-, and [1,1,2,2,3,3,3-D ]-n-prop-
anols were made by reduction of the corresponding acids with LiAlH
or LiAlD , respectively. Catalytic reduction of unlabeled and [1-D ]-
prop-2-en-1-ol with deuterium afforded [2,3-D ]- and [1,2,3-D ]-n-
propanols, respectively; the labeled allyl alcohol was made by
2
O.
2
3
5
7
4
4
1
Large aromatic macrocyclic compounds such as porphyrins
and phthalocyanines have attracted the interest of many
chemists.[ In the phthalocyanine family, naphthalocyanines
are important analogues and have been used in commercial
fields such as read/write compact discs. Although not often
used in practice, perhaps the next best known phthalocyanine
analogues are hemiporphyrazines, which can be obtained by
2
3
1, 2]
reduction of acrolein with LiAlD
4
. [3,3-D
2
]- and [3,3,3-D
3
]-n-prop-
I
anols were prepared by Cu -catalyzed addition of the corresponding
methyl Grignard reagents to ethylene oxide. Except the preparation
of [1,1,1-D
labeled isopropanols were made by reduction of acetone, [D
,3-dichloroacetone, and [1,1,3,3-D ]-1,3-dichloroacetone with LiAlH
or LiAlD , respectively.
3
]isopropanol by addition of CD
3
MgI to acetaldehyde, all
6
]acetone,
1
4
4
the condensation reaction of equimolar amounts of 1H-
4
3]
[
8] The experiments were performed with a modified VG ZAB/HF/
AMD four-sector mass spectrometer of BEBE configuration (B
stands for magnetic and E for electric sectors) which has been
isoindole-1,3(2H)-diimines
and
2,6-diaminopyridines.[
Around a decade ago, a new member, synthesized from 1H-
isoindole-1,3(2H)-diimines and 2,5-diamino-1,3,4-triazoles,
was introduced into this family, and now such hemiporphyr-
azines are conventionally known as triazole hemiporphyr-
described previously.[ Briefly, propanol/Fe complexes were gener-
9]
5
ated by chemical ionization of a mixture of [Fe(CO) ] and the
corresponding propanol. The ions were accelerated to 8 keV kinetic
energy and mass-selected by means of B(1)/E(1) at a resolution of
m/Dm ꢀ 3000. Unimolecular fragmentations of metastable ions occur-
ring in the field-free region preceding B(2) were recorded by scanning
this sector. A total of 10 to 30 scans were averaged to improve the
signal-to-noise-ratio, and the data are the averages of at least three
independent measurements.
[4]
azine 3 (Scheme 1). These compounds are cyclic tetramers
tBu
N N
S
tBu
S
tBu
tBu
N
N
N
N
N N
[
9] C. A. Schalley, D. Schröder, H. Schwarz, Int. J. Mass Spectrom. Ion
Processes 1996, 153, 173.
10] This criticism includes our own work, for example: a) S. Karrass, T.
Prüsse, K. Eller, H. Schwarz, J. Am. Chem. Soc. 1989, 111, 9018; b) D.
Schröder, W. Zummack, H. Schwarz, J. Am. Chem. Soc. 1994, 116,
NH
HN
NH
HN
N
N
N
N
N
N
[
S
N
S
N
N
N
N
N
N
N
S
H
N
S
H
N
N
N
5857; c) R. Wesendrup, C. A. Schalley, D. Schröder, H. Schwarz,
Organometallics 1996, 15, 1435.
[
[
[
11] The details of the algebraic formalisms used as well as a sensitivity
analysis will be reported in a full article; they are available from
Claudia.Trage@www.chem.tu-berlin.de.
12] Note that secondary kinetic isotope effects need not be considered
explicitly, because they are either inherently included in the analysis
tBu
tBu
1a
1b
tBu
tBu
N N
S
2
or cancel out in the H O/HDO ratios.
13] Additional information, which will be presented in a full article,
N
N
tBu
tBu
suggests that the C�O bond insertion 1 !2 is also quasi-irreversible
NH
HN
N NH
N
for the metastable ions. This conclusion is further supported by the
N
N
N
N
N
N
substantial barrier predicted for the insertion of Fe into the C�O
S
N
S
N
N
N
N
N
bond of methanol.[
14]
H
N
NH
HN
[
[
[
[
14] Y. Shiota, K. Yoshizawa, J. Am. Chem. Soc. 2000, 122, 12317, and
N
references therein.
HN N
15] See also: D. Schröder, C. Trage, H. Schwarz, D. Danovich, D. Shaik,
Int. J. Mass Spectrom. 2000, 200, 163.
16] Review: J. M. Brown, Angew. Chem. 1987, 99, 169; Angew. Chem. Int.
Ed. Engl. 1987, 26, 190.
17] a) Review: H.-H. Brintzinger, D. Fischer, R. Mühlhaupt, B. Rieger, R.
Waymouth, Angew. Chem. 1995, 107, 1255; Angew. Chem. Int. Ed.
Engl. 1995, 34, 1143; b) D. J. Tempel, L. K. Johnson, R. L. Huff, P. S.
White, M. Brookhart, J. Am. Chem. Soc. 2000, 122, 6686.
tBu
tBu
2
3
Scheme 1. Two possible structures 1a and 1b for the condensation
products of 2,5-diamino-1,3,4-thiadiazole and 5-tert-butylisoindolediimine,
and a possible structure for compound 2. The triazole hemiporphyrazine
structure is shown at the bottom right.
[*] Prof. Dr. Dr. N. Kobayashi, S. Inagaki, Dr. V. N. Nemykin,
Dr. T. Nonomura
Department of Chemistry
Graduate School of Science, Tohoku University
Sendai 980-8578 (Japan)
Fax : (81)22-217-7719
E-mail: nagaok@mail.cc.tohoku.ac.jp
[
**] This work was supported partly by a Grant-in-Aid for Scientific
Research (B) No. 11440192 and the Shorai Foundation for Science &
Technology.
Supporting information for this article is available on the WWW under
http://www.angewandte.com or from the author.
2710
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
1433-7851/01/4014-2710 $ 17.50+.50/0
Angew. Chem. Int. Ed. 2001, 40, No. 14