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The First Clusters with a Y-Shaped Arrangement of Ligands at Three-Coordinate RhI Atoms in the Solid State [M1M2{-P(C6H11)2}(CO)8Rh(PPh3)] (M1 M2 = Mn Re).

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(dicarboximides) are green both in the solid state and in concentrated solutions. At the concentrations required for UV spectroscopy, L = lo-' M, the solutions are largely colorless. Similarly, films of 14 spin-coated onto quartz are also colorless. To
compare the aryl- and alkyl-substituted quaterrylenes 9 and 10,
their spectra were measured in sulfuric acid/oleum. Both compounds have unusual but identical UV spectra in the NIR region
with only a single very sharp peak (J-band['4'). Particularly
remarkable is the extremely high extinction ( E = 654705) of the
band at 876 nm (10, Fig. 2). The identical behavior of 9 and 10
may be used as supporting evidence for the structure of the alkyl
derivatives which are not soluble in organic solvents.
Hans-Gunther Beckers, Ulrich Florke,
and Hans-Jurgen Haupt*
Fig. 2 . Electronic absorption spectrum of 10 in H,SO,/oleum (57%) (4: I )
According to thermogravimetric investigations, the stabilities
of 9, 10, and 14 (no decomposition up to 480 "C) correspond to
those of the known perylenebis(dicarb0ximides) . The important
contributor to the thermal stability of the perylenebis(dicarb0ximides) is only, therefore, the type of N-substitution; the mass
loss determined corresponds exactly to the loss of the substituent on the N atom.
The markcd absorption in the region 764 to 782 nm in this
system has particular advantages since it can be used in many
optical applications in conjunction with commercially available
GaAlAs lasers which emit at 780 nm. This is a necessary prerequisite, for example, for applications in optical data storage systems. Future investigations will aim at extending applications to
semiconductors and thermal liquid crystal displays.
Received: January 20. 1995 [Z76471E]
German version: Angew. Chem. 1995. 107, 1487-1489
Keywords: arenes . carboximides dyes . perylenes . UV spectroscopy
14. 295.
The First Clusters with a Y-Shaped Arrangement
of Ligands at Three-Coordinate Rh' Atoms
in the Solid State:
[M1M2{P-P(C,H, 1)2)(CO),Rh(PPh,)l
(M1, M2 = Mn, Re)**
1121 T. Yamamoto, A. Morita. Y. Miyazaki. T. Maruyama, H . Wakayama, Z. Zhou,
Y Nakamura, T, Kanbara, MacromolwuLP 1992, 25. 1214.
[I31 W. Bradley, F. W. Pexton, J Chrm. Sue. 1954, 4432.
[I41 The J-band results from the formation of aggregates and is observed for polymethine dyes, in particular. In the case of quaterrylenebis(dicarboximides)this
behavior can be explained by protonation of the chromophore. a) G . Scheibe.
Ku//u~d-Z.1938. 1. b) K. Norland, A. Ames, T. Taylor, Phor. Sci. Engl. 1970,
[ ~ - l c .m
[lo] We would like to thank BASF A G for donating a sample o f M-(7.6-diisopropylphenyl)-3,4-perylenedicarboximide (4).
[ I l l Y. Nagao. Y Abe. T. Misono. Dyrs P i p . 1991, 16, 19.
F. Graser. E. Hldicke. L i e h g . Ann. Chem. 1980, 1994; rhid. 1984. 483.
Y. Nagao. T. Misono, D y s Pigm. 1984, 5, 171.
A. Rademacher, S. MHrkle, H. Langhals, Chem. Ber. 1982, 1 IS, 2927.
H . 0. Loutfy. A. M. Hor. P. Kazmaler, M. Tam. J. Imaging Sci.1989,33, 151.
G . Seybold. G. Wagenblast. Dye.! Pigm. 1989, I f , 303. H. Langhals, Nuchr.
Chm7. Terh.Luh. 1980, 28, 716.
D. Schletlwein, D., E. Karmann, U. Melville, Chem. Murer. 1994.6.3.
M. P. O'Neil, M . P. Niemczyk, W. A. Svec. D. Gosztola, G. L. Gaines 111,
M . R. Wasielewski. Sciiwce 1992, 257, 63.
J. Fabian, R Zahradnik, Angew Chem. 1989, 1 0 / . 693; A n p w Chem. I n f . Ed
1989. 2X. 677.
Y Nagao. T. Misono. Bull. Chem. Sue. Jp7. 1981. 54. 1191.
Angrn.. Chwn In[. Ed. Engl. 1995, 34, N u . 12
According to kinetic studies by Halpern et al.,"] during the
homogeneously catalyzed hydrogenation of alkenes, complex
fragments are formed from the Wilkinson catalyst [RhCl(PPhJ,] by dissociation that contain three-coordinate Rh' atoms.
Corresponding species should also be produced in solution during the thermal decomposition (-70 "C) of [RhH(N,)(PR,),]
complexes with sterically demanding phosphane ligands
In the solid
(R = Bu, cyclohexyl (Cy)) by the release of N2(g).[21
state, however, a coordination number of 3 for a central d8
rhodium(1) atom is unusual and has only been described for the
diamagnetic, red complex cation [Rh(PPh,),]+ in salts with
various anions (CIO;, [nido-7-(1-closo-1,2-C,B,,H, ,)-73C,B,H, J - ) . [ 3 , 41 According to the X-ray structure analysis, the
three covalent Rh-P bonds are arranged in a T formation. For
the perchlorate salt, this ground state geometry is stabilized by
the attractive Rh . . . H interactions with a concomitant weakening of the Lewis acid strength of the central atom.r3.'] Futhermore, the rigidity of the cation in non-coordinating solvents was
verified by 31PDNMR spectroscopy.[61Spin coupling data between ' 03Rh and 'P from temperature-dependent experiments
indicate that an intramolecular exchange of the phosphane ligands takes place. This would occur, in agreement with MO
calculations, via a Y-shaped intermediate ( C 3 *.['.
Instead of
using sterically demanding ligands we attempted to produce
threefold coordination by the inclusion of a ligand-stabilized
Rh' center into a bond system capable of mesomerism. In the
light of our work on rr-bonding properties of c y l o - M , and
tetuahedro-M, clusters, we decided to join suitable anionic phosphido-bridged binuclear complexes with rhodium(1) complex
cations using a so-called redox condensation.", '.
The title compounds 3 and 4 were obtained from hydridophosphido-bridged binuclear complexes of metals from
group nine [9. l o , 12] in a three-step synthesis as summarized in
Scheme 1 : 1) deprotonation by a non-nucleophilic base, 2) "redox condensation", and 3) selective oxidative removal of a Rhbound CO ligand. The analogous Mn,Rh cluster 5 was obtained
Prof. Dr. H:J. Haupt, Dipl.-Chem. H:G. Beckers, Dr. U. Florke
Anorganische und Analytische Chemie der Unversitit-Gesamthochschule
Warburger Strasse 100. D-33098 Paderhorn (Germany)
Telefax: Int. code + (5251)603-423
VCH VerlugvgesellscAuft mhH, 0-69451 Weinheim, 1995
flS70-0833/Y51/212-1325 $ 10.00 i
I DBU, THF. 200C
2 PPhqBr
MIO=) ~
] M2 = Re, 1; MI = M2 = Re
= Mn,M2 = Re,
2; MI
[ M I M ~ ( , U - P C ~ ~ ) ( C ~ ) ~ R MI
~ ( P= PMn,
~ ~ Mz
) ] = Re. 3; MI
= M2 =
M2 = Re, 4
Scheme 1.
by a somewhat modified synthesis.["] On swapping Rhl for Ir',
reaction step 3 did not produce any corresponding clusters of
the title compounds. The molecular structures of the two precursors [M'MZ(p-PCy2)(CO),Rh(CO),(PPh3)],
namely the
cyclo-Re,Rh cluster (M' = M2 = Re) and 2 (MI = Mn,
M2 = Re), have been established by single-crystal X-ray diffraction.[*. 12] They differ in that one of the terminal CO groups
on the Rh' atom in the Re,Rh cluster is in a semi-bridging
position towards the manganese atom in compound 2.
The molecular structures of 3-5 were solved by single-crystal
X-ray analysis['31 (Fig. 1 ) . The central molecular fragment is a
three-membered ring consisting of MnReRh in 3, Re,Rh in 4,
Fig. 1. Molecular structure of 3 (M' = M 2 = Mn.Re), 4 (M' = M 2 = Re) and 5
(M' = M 2 = Mn). Important bond lengths [A] and angles ["I: for 3: Ml-M2
3.164(1), M1-Rh 2.785(1). M2-Rh 2.760(1), MI-PI 2.375(2), M2-Pl 2.391(2); M1Rh-M2 69.59(2). M1-Rh-P2 135.42(5), M2-Rh-P2 153.65(5). Rh-MI-M2 54.83(2),
Rh-MZ-Ml 55.58(2), MI-PI-M2 83.20(6); for 4: Rel-Re2 3.199(1), Rel-Rh
2.834(1), Re2-Rh 2.819(1), Rel-PI 2.435(2), Re2-P1 2.443(2); Rel-Rh-Re2
68.93(3). Rel-Rh-P2 151.65(5), Re2-Rh-P2 136.20(5). Rh-Rel-Re2 55.32(2), RhRe2-Re1 55.75(2), Rel-P1-Re2 81.96(6); for 5 : Mnl-Mn2 3.060(2). Mnl-Rh
2.727(1), Mn2-Rh 2.689(1), Mnl-P1 2.301(2), Mn2-PI 2.310(2): Mnl-Rh-Mn2
68.80(3), Mnl-Rh-P2 135.8815). Mn2-Rh-P2 153.96(5). Rh-Mnl-Mn2 55.02(3).
Rh-Mn2-Mnl 56.17(3). Mnl-P1-Mn2 83.17(6).
Vrrkrgsgesellscliaft mhH. 0-69451 Weinheini, 1995
and Mn,Rh in 5. The Rh' atom coordinates with both metal
atoms of group nine to give an acute bond angle (69.59(2)' in 3,
68.93(3)" in 4,and 68.80(3)" in 5 ) and with the phosphorus atom
in the PPh, ligands to give differing obtuse bond angles (P(2)Rh-M(1) 135.4(1), P(2)-Rh-M(2) 153.7(1)" in 3; 136.2(1),
151.7(1)" in 4; 135.9(1), 154.0(1)" in 5 ) . Such varying bond
angles are also found in precursors with five-coordinate Rh'
and are therefore independent of the coordination
number. Consequently, the Rh' atom in the three structurally
analogous cyclu-M, clusters is, in each case, coordinated in a
distorted Y-shaped, almost planar manner; the smaller of the
two exocyclic bond angles always occurs on the longer Rhtransition metal bond. This differentiation leads to a quasi trans
positioning of the Rh-P bond towards the shorter Rh-M bond
in 4 and 5 (a thermodynamic trans effect). The resulting significant shortening of the Rh-M bond is 0.025(1)A in 3,
0.01 5(1) 8, in 4,and 0.038(1) A in 5.Because compounds 3-5 do
not show any unusual distances between neighboring ligands
along the two Rh-M bonds, and they crystallize in different
crystal systems, the Y-shaped coordination geometry at the Rh'
atom is not influenced by either repulsive interactions of neighboring ligands or by packing effects. In contrast to the ideal D,,
geometry of a [Rh'L,] complex, both this new Y-shaped as well
as the previously described T-shaped coordination geometry
(ideally Czv)at the Rh' atom allows the removal of the degeneracy of the e' orbital set that is occupied by two valence electrons.
This explains the diamagnetism of compounds 3-5. Not only
the P atom of the bridging dicyclohexylphosphido group but
also the Y-coordinated Rh' atom is a component of an edgesharing coordination dioctahedron of the two transition metal
atoms. There are no distortions of the coordination geometry
when compared to the structures of similar heteronuclear cycluM, clusters.[7.*, 'I From this, it follows that in the molecular
fragment [M'M2(p-PCy,)(CO),] (M' -M2, d7-d') of the cycluM, cluster the covalent bonds to the Rh' atom are formed over
centered as well as over edge-sharing frontier orbitals, as was
already postulated by MO calculations on related
If the fragment is considered to be an anionic two-electron
donor ligand, the Rh' atom (d') with the PPh, ligand has the
same number of donor electrons, that is formally only 12 valence electrons as opposed to the usual 14 and 16 valence electrons in the compounds known to date. This obvious electron
deficiency on the Rh atom is compensated by n-electron delocalization along the two Rh-M bonds. Therefore these are shorter
than the corresponding covalent single bonds. This is demonstrated by the following comparisons which, on the one hand,
show a shortening of the Rh-M bonds in 3-5 compared to o
bonds. and on the other hand, a lengthening compared to 7c
bonds in other similar compounds. Thus, in 4 the Rh-Rh distance is 2.827(1) A (average value), whilst for [(PCy,),ReH(p-PCy,),Rh(l ,5-cod)][BF4] (cod = cyclooctadiene) with diphosphido-bridged metal centers, a Re-Rh distance of
for a 0 bond is observed. In the hydridosulfidobridged compound [RhRe(CO),(p-H)(p-SEt)(dppm),l(dppm =
bis(dipheny1phosphano)methane) the Re-Rh (3 bond length
is 2.9697(8)A.r'61 In comparison, the Re-Rh R bond in
[Re,Rh(p-CO),(p-PCy,)(CO),(PPh,),]is 2.681(1)
Likewise, the Mn-Rh bond in 5 (mean 2.708(1) A) is shorter than
the Mn-Rh G bond in [MnRh(CO),(dppm),] (2.843(1) A)[171
and longer than the Mn-Rh n bond in [ReMnRh(p-CO),(p-PCy,)(CO),(PPh,),] (2.585(2) A).[12]Therefore, the Rh-M
bond lengths found for the title compounds lie in the range of a
bond order of 1.5, which corresponds to a n-electron delocalization in the M'-Rh-M2 ring. This effect undoubtedly reduces the
strength of the M'-MZ bond, so that the M'-M2 bonds in 3,
o57O-os33/95/i212-1326$ 10.00+ .25/0
Angrw. Cliem. Int. Ed. Engl. 1995, 34, No. 12
4, and 5 are longer than the corresponding bonds in compounds
of the type [MtM2(p-H)(p-PCy,)(CO),1 Similar results have
been found for the mercury atom in the cyclo-M, compound
Because the rhodium(1) atom in 3-5 has one or two free
coordination sites for two-electron donors, we were also interested in the homogeneous catalytic properties of these compounds. However. attempts at homogeneous catalytic hydrogenation with 4 or 5 as the catalyst in dioxane were unsucessful
(10 bar H 2 . 1-hexene, I O O T , 12 h); only metal deposition was
observed in each case. Consequently, the transitions between 16
and 18 valence electrons, which are typical for a catalytic hydrogenation cycle with Rh' complexes, cannot be obtained with the
title compounds because the activation barrier is too high.
Therefore. the three-coordinate Rh' atom only appears to be an
active homogeneous catalyst if it is not a particularly strong
Lewis acid. This argumentation is supported by our observations that the similar cy/o-M, cluster [MtM2(p-PCy2)Rh(p-CO),(PPh,)(CO),] (MI, M2 = Mn. Re) with (4 + 2)-fold
coordination of the Rh' atom is catalytically active under
analogous reaction conditions ( T H E 3 bar H,, 3 bar CO, 60 "C,
1-hexene) .I1 For example, TON values of approximately
100 h - ' were obtained with an Mn,Rh compound in an 0x0
reaction.['*' To date. this could not be even nearly achieved with
19] The Rh'
a soluble heteronuclear Rh cluster as the
atom shows in the cited cyc/o-M3 clusters a rarely observed
(4 + 2) coordination.['' Therefore, in the Rh' complex fragments bound in the clusters the decisive factor for the interplay
between 16 and 18 valence electron species in the catalytic cycle
and for the catalytic efficiency is not the threefold coordination
of the Rh' atom, but the type of ligands and the symmetry of
their spatial arrangement. Such considerations are important
for the development of new Rh' catalysts.
FT-IR spectra (Nicolet P510) of the new compounds were recorded. unless otherwise stated. in CH,CI, in the range 2200 to I600 c m - ' for v ( C 0 ) absorption bands.
"P NMR spectra (Bruker AMX 300) were recorded in CDCI, with 85% H,PO, as
the external standard. Solvents used were distilled twice, dried, and stored under
argon. All reactions were carried out under argon.
I : [MnRe(ir-H)(,i-PCy,)(CO)J (663 mg, 1 mmol) [9] in T H F (20 mL) was deprotonated with 1,8-diazabicyclo[S.4.O]undec-7-ene
(DBU) (300 mL, 2 mmol) a t 20°C in
4 h. To isolate the product. the solvent was evaporated. the residue dissolved in
C,H,OH (10 mL), and PPh,Br (545 mg, 1.3 mmol) added. Compound 1 was precipitated by addition of oxygen-free water (50 mL), filtered off, and washed with
water (3 x 1 5 mL) followed by ti-hexane ( 3 x 15 mL). Yield: 940 mg (94%) of airstable. yellow, complex salt.
2: Equimolar amounts of 1 (100 mg. 0.1 mmol) and [RhCO(PPh,),]CI (69 mg.
0.1 mmol) were dissolved in CO-saturated T H F at 0 ° C and TIPF, (419mg.
1.2 mmol) was added as a halogen trap. The reaction solution immediately turned
deep red and was allowed to warm to 20'C over 2 h in a weak flow of CO,,,. To
isolate the product. the T H F was removed and the solid residue dissolved in
CH,CI,. the solution was filtered through Celite and the components separated by
thick layer chromatography using CH,Cl,/n-hexane (1/3) as the eluent. Yield:
74 mg (69%) of red solid.
3: 2 (108 mg. 0.1 mmol) in T H F (15 mL) was treated with Me,NO (8.3 mg,
0.1 1 mmol) at 0 C and the reaction mixture was allowed to warm to 20 "C over 2 h,
during which time the color of the solution changed from red to yellow. To isolate
the product the T H F was removed, the solid residue dissolved in a small amount of
acetone. the solution filtered through basic AI,O, and the product separated chromatographically and crystallized with CH,Cl,/hexane (l/S). Yield: 83 mg (80%) of
yellow product.
4: In an analogous procedure to that used for 1 from [Re2(p-H)(/i-PCy2)(Co),l
(794 mg. 1 inmol) [lo]. DBU (450mL. 3 mmol), and PPh,Br (545 mg. 1.3 mmol)
produced PPh,[Re,(/i-PCy,)(CO),) (1008 mg, 95 "A).The reaction of this salt
(1 13 mg. 0.1 mnml) with [Rh(CO)(PPh,),]CI (69 mg. 0.1 mmol)[ll] under the same
conditions applicd for complex 2. gave [Re(p-PCy,)(CO),Rh(CO),(PPh,)l[XI.
Treatment of the latter (118 mg. 0.1 mmol) with Me,NO (8.3 mg, 0.1 mmol) in an
analogous way to that used for 3 gave the pale yellow product 4 (99 mg, 85%).
Compounds I- 4 and PPh,[Re,(/i-PCy,)(C0),1 gave correct C.H analysis (Automat
PE 240). IR (CH,COCH,): I - C(C0) = 2039m. 1971 s, 1936vs, 1905s. 1888s;
1 8 7 1 s c m - ' : 2: i.(CO)=2079w. 2035m. 2 0 1 5 ~ 1998~s. 1946s. 1898m
(br.)cm-'; 3: i ( C O ) = 2 0 1 3 s 1973vs. 1944s. 1921 5 c m - I ; PPh,[Re,(/iPCy,)(CO),]: i ( C 0 ) = 2042m. 1988 m. 1936 vs. I911 m, 18x8 s. 1x73 hem-'; 4:
F(CO) = 2033 s. 1977 vs, 1950 s, 1921 s c m - ' ; UV-Vis (Perkiii-Elmer-Lambda-15,
CH,CI,)- 3: imaX(&)
= 338 (817), 392 nm (359m'mol-I): 4 . i.,,,dx(c) = 323 (773),
359 (522 m'mmol~': "P-NMR (CDCI,): 1: 6 = I 5 6 7 (s. 1i-P). 23.7 (s, PPh,): 2:
d = 215.1 (s, f1-P). 35.1 (d, 'J(P,Rh) =147 Hz): 3 : d = 177 9 (5. p P ) . 18.5 (d,
'J(P.Rh) = 322 Hz); PPh,[Re,(p-PCy,)(CO)8]: d = 101.4 (a. 11-P),23.7 (s, PPh,); 4:
6 =124.5 (s. 11-p). 21.1 (d. 'J(P.Rh) = 352 Hz).
Received: January 28. 1995 [Z7671 IE]
German version: Angew. Chem. 1995. 107, 1464-1466
Keywords: catalysis
clusters . coordination . rhodium com-
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U. Florke. H:G. Beckers. H.-J. Haupt, Z.Km.,sra//ogr.,in press.
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H:G. Beckers. Dissertation. Universit~t-GesamthochschulePaderborn. 1995.
Crystal structure analysis of 3 . orange-red crystal. 0.39 x 0 44 x 0.50 mm, monoclinic, space group PZ,/n. u =11.122(3). h = 12.929(3). c = 28.761(8) A,
p = 99.69(2)", V = 4077(2) A3, Z = 4. pLdlid= 1.674 gcm /I = 3.79 m m - I ,
3 5 20 5 55". Mo,, radiation. E. = 0.71073 A, 4 2 0 scan, 298 K, 9508 measured reflections. 9333 independent, of which 6637 with F > 4 u ( F ) ,empirical
absorption correction with $-scans, min./max. transmission 0.680/0.956. structure solved by direct and conventional Fourier methods, full matrix leastsquares refinement based on F 2 and 458 parameters, all non-hydrogen atoms
anisotropic. H atoms in idealized positions (riding model). Re and Mn are
disordered on the metal positions M1: 0.46 Re, 0.54 Mn and M2: = 0.54 Re,
0.46 Mn. one cyclohexyl group is disordered over two positions each with an
occupation factor of 0.5, R I ( F ) = 0.053, w R 2 ( F 2 ) = 0.166. Crystal structure
analysis of 4.0.5(CH3),CO: yellow crystal, 0.35 x 0.43 x 0.52 mm, triclinic.
space group P i . u =10.438(4). h =14.385(5), c =14.619(5) A. x =107.01(2),
p = 90.22(2), I; = 97.23(2)'. V = 2080(1) A', Z = 2. pcA,c,,= 1.896 g ~ m - ~ .
p = 6.39 m m - l , data collection as for 3,9954 measured reflections, 9585 independent, of which 7698 with F > 4u(F), correction as above, min-imax. transmission 0.666/0.896, structure solved and refined as above. 488 parameters,
Rl(F) = 0.047, wR2(F2)= 0.124. Crystal structure analysis of 5 : yellow crystal. 0.20 x 0.33 x 0.45 mm, monoclinic, space group P2,jn. a = 11.023(2),
h =12.918(4), c = 28.534(7) A, fi = 99.70(2)', V = 4005(2) A', Z = 4,
=1.487gcm-'.p =l.l56mm-'.datacollectionasfor3. 9387measured
reflections. 9212 independent. of which SO63 with F > 4u(F), corrections as
above. min./max. transmission 0.743!0.867, structure solved and refined as
above. 471 parameters, one carbonyl and one cyclohexyl group are disordered
over two positions. each with an occupation factor of 0.5, Rl(F) = 0.061.
krR2(F2)= 0.173. Programs used: SHELXTL-Plus,[20] SHELXL-93 [21].
Further details of the crystal structure investigations may he obtained from the
Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen
(Germany) on quoting the depository numbers CSD-401484 (3), CSD-401485
(4). and CSD-401486 ( 5 ) .
[I41 T. A. Albright, S.-K. Kang, A. M. Arif, A. M. Bord, R. J. Jones, J. K. Leland,
S. T. Schwab. Inorg. Chem. 1988,27. 1246-1253.
[15] R. T. Baker, J. C. Calabrese. T. E. Glassman, Orgunomerul/ic.\ 1988, 7, 18891891.
[I61 D. M. Antonelli, M . Cowie, Inorg. Chern. 1990, 29, 3339 3345.
[I71 D. M. Antonelli, M. Cowie, OrganomeruNics 1990, 9. 1818- 1826.
[18] J. S. Bradley, Clustus and CoNoids - From Theory to App/icurions (Ed.: G.
Schmid). VCH, Weinheim, 1994, p. 523-524.
[I91 R. D. Adam% The Chemisrry o f' A 4 e d C/zorer.Comnp/e.w$(Hrsg.: D. F. Shriver,
H. D. Kaesz, R. D. Adams). VCH, Weinheiin, 1990, p. 121-165.
[20] G. M. Sheldrick, SHELXTL-Plus, Siemens Analytical X-ray Instruments,
Madison, WI, USA, 1991.
[21] G. M. Sheldrick. SHELXL-93, Program for Crystal Structure Refinement,
Universitit Gottingen, 1993.
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