Communications
7.7 mmol). The solution was stirred 0.5 h at À788C and then
P. von Rague Schleyer), Wiley-Interscience, New York, 1995,
p. 295.
another 5 h at RT. The resulting solution was added dropwise at
¼
[18] M. Melnik, L. Macaskova, C. E. Holloway, Coord. Chem. Rev.
1993, 126, 71 92.
À788C to a solution of ClP C(SiMe3)2 (1.74 g 7.7 mmol) in
diethyl ether (30 mL). After stirring for 1 h at low temperature
the solvent was removed under reduced pressure. The residue
dissolved in n-hexane and then filtrated. After concentration of
the filtrate solution 1a precipitates in crystalline form as
isomeric mixture rac/meso-1a ¼ 4:1. MS (16 eV): m/z (%) ¼
636 (8) [M]þ, 562 (66) [MÀSiMe3]þ, 73 (100) [SiMe3]þ;
31P NMR(CH2Cl2, 258C): d ¼ 386.2, 388.1 ppm (rac/meso-1a).
[11] a) D. Jerchel, S. Noetzel, K. Thomas, Chem. Ber. 1960, 93, 2966
2970; b) M. D. Rausch, D. J. Ciapenelli, J. Organomet. Chem.
1967, 10, 127 136.
[19] CuI-complexes of diazapyridinophanes do not display geome-
tries that are comparable to 6; H. J. Kr¸ger, personal commu-
nication.
[20] The polarized UV/Vis absorption spectra were recorded using a
particular micro single-crystal UV/Vis spectrometer. Details
about this instrument are prevalent in the literature: E. Krausz,
Aust. J. Chem. 1993, 46, 1041 1054. The investigated crystal of
compound 6 had a cross-section of 0.20 î 0.08 mm2, (thickness
0.05 mm), the crystal of compound 4 was notably smaller with a
cross-section of 0.10 î 0.05 mm2 (thickness ¼ 0.05 mm).
[21] J. Grobe, N. Krummen, R. Wehmschulte, B. Krebs, M. L‰ge, Z.
Anorg. Allg. Chem. 1994, 620, 1645 1658.
[12] The free l-N2P2[CH(SiMe3)2]2 ligand 4 prefers a syn-chair-chair
conformation in the solid state.[8] The ligand 5 retains the
conformation of the ate-complex 3. S. Ekici, M. Nieger, E.
Niecke, unpublished results.
[22] CV: v ¼ 200 mVsÀ1; CH2Cl2/nBu4NBF4 0.1m; calomel/GCE/Pt
(GCE ¼ glassy carbon electrode). MeCN/nBu4NPF6; reference
electrode: calomel E ¼ 0.24 V; IR-compensation (kW) 3: 2.5; 5,
6: 0.2; 7: 4.5.
[13] H. J. Kr¸ger, Chem. Ber. 1995, 128, 531 539.
[14] Selected bond lengths [pm] and angles [8] of 2. Li1-N1 209.7(8),
Li1-N33 211.8(7), Li1-P1 244.5(7), Li1-P2 250.1(7); N1-Li1-N33
86.9(3), N1-Li1-P1 87.3(3), N1-Li1-P2 86.9(3), N33-Li1-P1
86.2(3), N33-Li1-P2 87.4(2), P1-Li1-P2 171.6(3). The analogous
phosphamethanide-complex bearing four SiMe3 groups instead
of the four phenyl groups in 2 has a similar structure.[9]
[15] Crystal data: 3: C55H115ClFeLi3N7P2Si6, Mr ¼ 1217.14, triclinic,
ꢀ
space group P1 (no. 2), a ¼ 13.6549(1), b ¼ 14.6901(2), c ¼
19.2675(2) ä, a ¼ 102.043(1), b ¼ 92.848(1), g ¼ 103.988(1)8,
V¼ 3647.28(7) ä3, Z ¼ 2, m(MoKa) ¼ 0.422 mmÀ1, F(000) ¼ 1320,
43173 reflections (2qmax ¼ 508), thereof 12849 unique, wR2(F2) ¼
0.1142, R(F) ¼ 0.0406, 670 parameters, 309 restraints. 2:
C72H106Li2N2O5Si4, Mr ¼ 1267.77; orthorhombic, space group
HRMAS NMR Spectroscopy
1
Application of HRMAS H NMR Spectroscopy
To Investigate Interactions between Ligands and
Synthetic Receptors**
P212121
(no. 19),
a ¼ 16.8587(2),
b ¼ 20.3906(3),
c ¼
21.2944(3) ä, V¼ 7320.1(2) ä3, Z ¼ 4, m(MoKa) ¼ 0.173 mmÀ1
,
F(000) ¼ 2736, 70978 reflections (2qmax. ¼ 508), thereof 12972
unique, wR2(F2) ¼ 0.2342, R(F) ¼ 0.0766, 759 parameters, 505
restraints. The absolute configuration could not be determined
Heidi H‰ndel, Elke Gesele, Klaus Gottschall, and
Klaus Albert*
þ
À
reliably (x ¼ 0.40(14)). 6: C52H68CuN2P2Si4 CF3SO3
,
Mr ¼
ꢀ
1107.99, triclinic, space group P1 (no. 2), a ¼ 11.2089(5), b ¼
15.2256(7), c ¼ 18.0123(10) ä, a ¼ 99.324(2), b ¼ 91.194(2), g ¼
Dedicated to Professor G¸nther Jung
on the occasion of his 65th birthday
111.352(2)8, V¼ 2814.5(2) ä3, Z ¼ 2, m(MoKa) ¼ 0.619 mmÀ1
,
F(000) ¼ 1164, 13085 reflections (2qmax. ¼ 508), thereof 9316
unique, wR2(F2) ¼ 0.2148, R(F) ¼ 0.0802, 606 parameters, 581
restraints (disordered CHTms2 groups). 7: C38H69NOP2Si6Fe-
Molecular recognition processes are predicted to become the
basis of all advanced separation techniques. The investigation
of intermolecular interactions in the interphase between a
chromatographic support and a substrate dissolved in a
mobile phase is the crucial condition for understanding
chromatographic separation mechanisms and for the design
of tailored stationary phases. In solution and also in suspen-
sion ligand receptor interactions can be studied using meth-
ods of high-resolution (HR) NMR spectroscopy, for example
by employing the nuclear Overhauser enhancement (NOE)
ꢀ
Ni¥Et2O, Mr ¼ 975.10, triclinic, space group P1 (no. 2), a ¼
15.0304(1), b ¼ 18.0995(2), c ¼ 20.0055(2) ä, a ¼ 85.709(1), b ¼
88.418(1), g ¼ 69.915(1)8, V¼ 5097.0(1) ä3, Z ¼ 4, m(MoKa) ¼
0.891 mmÀ1
,
F(000) ¼ 2088, 65240 reflections (2qmax ¼ 508),
thereof 17943 unique, wR2(F2) ¼ 0.1170, R(F) ¼ 0.0424, 986
parameters, 92 restraints (disordered solvent Et2O). All struc-
ture data were collected on a Nonius KappaCCD diffractometer
using MoKa-radiation. The structures were solved by direct
methods (SHELXS-97) and refined anistropically on F2, the H-
atoms were refined using a riding model (SHELXL-97). CCDC-
181615 (2), CCDC-181616 (3), CCDC-190910 (6), and CCDC-
190911 (7) contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge via
bridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB21EZ, UK; fax: (þ 44)1223-336-033; or deposit
@ccdc.cam.ac.uk). SHELXS-97: G. M. Sheldrick, Acta Crystal-
logr. Sect. A 1990, 46, 467 473 SHELXL-97: G. M. Sheldrick,
Universit‰t Gˆttingen, 1997.
[*] Prof. Dr. K. Albert, Dr. H. H‰ndel, Dr. E. Gesele
Institut f¸r Organische Chemie
Universit‰t T¸bingen
Auf der Morgenstelle 18, 72076 T¸bingen (Germany)
Fax: (þ49)7071-295-875
E-mail: klaus.albert@uni-tuebingen.de
Dr. K. Gottschall
Dr. Gottschall INSTRUCTION
Gesellschaft f¸r Technische Chromatographie mbH
Donnersbergweg 1, 67059 Ludwigshafen (Germany)
[16] a) H. H. Karsch, G. M¸ller, J. Chem. Soc. Chem. Commun. 1984,
569 570; b) W. Clegg, S. Doherty, K. Izod, P. O©Shaughnessy,
Chem. Commun. 1998, 1129 1130, and references therein.
[17] ™Structures of Lithium Salts of Heteroatom Compounds∫: F.
Pauer, P. P. Power in Lithium Chemistry (Eds.: A.-M. Saspe,
[**] Thiswork wasfunded by Dr. Gottschall INSTRUCTION mbH,
Ludwigshafen. HRMAS¼high-resolution magic-angle spinning.
438
¹ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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