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Indigo-Metal Complexes Synthesis and Structure of PdII and PtII Compounds Containing the Anions of Indigo and Octahydroindigo as Mono- and Bis-Chelate Ligands.

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C1'-05': 48(2)"; HlO-C10-C1'-05':158"] reveal deviations
from the staggered arrangement of about 15", which may be
a result of repulsion between H5 and H2'.
The crystal packing (Fig. 2) shows channels at least 4 8, in
diameter along the c axis, where no atoms were found. The
volume defined by such a channel is sufficient to permit
incorporation of at least five positionally disordered water
molecules. The resulting disorder within the channel is transmitted to some extent to adjacent atoms in the aloin B molecule (C15.C3',02',03', and 04').
Establishment of the configuration at C10 of aloin B as R
simultaneously defines the configuration of aloin A
(1OS.l'S). Since the two substances may be regarded as parent structures for other naturally occuring diastereomeric
10-glucosylanthrones they should prove useful for making
future comparisons within this class of compounds.
scribed as "probably the most difficult structure proof to
that point accomplished"."b1 The existence of chelate complexes ML, 1 ( M = N i 2 @ ,Co2@,Cu2@,ZnZ@;L = m onoanion of indigo and certain derivatives) was demonstrated
~ ]far as we
by Kunz''] as well as by Kuhn and M a c h ~ m e r . [So
are aware, however, little attention has been paid to these
complexes since 1930.[41
The complexes I show little solubility in organic solvents.
Despite numerous attempts we were unable to prepare crystals that were suitable for X-ray analysis. The synthesis of
soluble, crystalline indigo complexes was finally accomplished by introduction of the ligand tri(n-buty1)phosphane.
Green chelate complexes 2 and 3, respectively, result from
Bu,P
\ /C'
Received: June 7, 1989 [Z 3382 IE]
German version: Angiw. Chm7. 101 (1989) 1539
111 Q. J. Groom. T. Reynolds. Plunro Mid. 53 (1987) 345- 348.
[2] T. Smith H. Smith. Phurn7. J 11 (1851) 23.
[4R. Eder. W. Zinn. Phurni. Acru H e h . 20 (1945) 410. 485.
141 H . Muhlemann. Phurm. Acru H r h . 27(1952) 17.
[ 5 ) M. Grun, G. Franz. Phurmaric. 34 (1979) 669.
I61 H. Auterhoff. E. Graf, G. Eurisch. M. Alexa, Arch. Phurm3/3 (Wcinhaim,
(1980) 113.
[7] H . W. Rauwald, K . Roth. Arch. Phurm. (Wc+iheim, Ger.) 3/7(1984) 362.
[8] H. W. Rauwald. Arch. Phurm. lWernh<,;m, Grr.) 315 (1982) 769.
191 M Grun. G. Frdnz, Arch. Phurm. (Weinheirn, G w . ) 315 (1982) 231 -241
[lo] Detail!, related t o the crystal structure analysis of aloin B I ( C 2 , H 2 2 0 9 ) :
yellow-brown. trigonal crystals from water/methanol, space group P321,
u = 17.67(1). c = 11.381(4)& V = 3079(5)A3. % = 6. Enraf-NoniusCAD4 diffr;ictometer. Cu,, radiation. 1474 independent reflections t o
2 0 = 110 very broad reflections, (0 scan with A(o = 9 R ( f ) = 0.164,
R,(I.) = 0.146 for 1187 reflections with I > ~ ( 0
structure
.
determination
by direct methods (SHELXS-86). hydrogen atoms o n C-atoms calculated,
those o n 0 - a t o m s not locaiized. S D P program system. The high R values
are a consequence of disordered solvent. The residual density is less than
0.6 e k' Further details of the crystal structure investigation are
available on request from the Fachinformationszentrum Karlsruhe.
Gesellschaft fur wissenschaftlich-technische Information mbH, D-7514
Eggcnstein-Leopoldshafen 2 (FRG). o n quoting the depository number
CSD-53855. the names of the authors, and the journal citation.
[I 11 F. R . Ahmed. Acru Crysfallo~r.B36 (1980) 3184.
1121 M. Whitefeld, K . Henrich. P. G. Owston. Actu Crwullogr. B38 (1982)
1248: E R. Ahmed. G . A. Neville. ihid. E38 (1982) 2930.
.
By Wolf&rng Beck *, Christoph Schmidt, Rolf Wienold,
Manfred Steimunn, and Barbara Wagner
Dedicated t o Professor Wolfgang Liittke on the occasion
of his 70th birthdq
It was Ado// von Bueyer, who, in Munich in 1883, firmly
established the structure of indigo""] in what has been de[*) Prof. Dr. w. Beck. Dip1:Chem. C. Schmidt, R. Wienold, M. Steimann [ '1.
Dip1:Chem
B. Wagner [ '1
lnstitut I'ur Anorganische Chemie der Universitit
Meiserstralk 1, D-8000 Munchen 2
X-ray structure analysis
This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie. We thank Prof. W Liifrkc.
Gottingen. for valuable suggestions and encouragement; H. Srhiinmunn.
Consortium fur elektrochemische Industrie GmbH, Munchen. for "Computer Molecular Modeling"; and BASF AG, Ludwigshafen, for chemicals.
Angew. Chrm. In!. Ed. Enxl. 28 ( t 9 8 9 ) N o . I 1
:M=Pd
2b:M=Fi
.
Indigo-Metal Complexes: Synthesis and Structure
of Pd" and Pt" Compounds Containing
the Anions of Indigo and Octahydroindigo
as Mono- and Bis-Chelate Ligands **
[ '1
[**I
2a
$3 VCH
PBUS
3
treatment of chlorine-bridged palladium(n) and platinum(ir)
compounds [(nBu,P)(Cl)M(p-CI)], ( M = Pd,Pt) with indigo
or octahydroindigo in THF in the presence of sodium hydride o r silver acetate.
Absorption bands in the UVjVIS spectrum of the complexes 2a and 3 show bathochromic shifts relative to those of
indigo itself.[51According to X-ray structural analyses, the
atoms palladium, imide nitrogen, and keto oxygen in 2 a
(Fig. 1) and 3 (Fig. 2) lie in nearly planar six-membered rings
(average deviation from planarity: 11 and 13 pm in 2a and
3, respectively). The monoanion of indigo functions as a
monochelate ligand in 2a, the dianion of octahydroindigo as
a bischelate ligand in 3. The four ligdnd atoms together with
the central Pd deviate from planarity up to 6 pm (2a) and
30 pm (3), respectively. The two planar five-membered
chelate rings are twisted out of the plane of the central C = C
bond by 9.6" (2a) and 15" (3). Replacement of the bridging
hydrogen atoms in indigof"' by Pd producei virtually no
change in the bond lengths in the five-membered rings o r in
the coordinated carbonyl groups (Table 1). The same is true
of a structurally related Pd" chelate complex of an a,P-ketoiminate.['I
It is interesting to note that the bond of the free carbonyl
group in 2a [C2-01 122.4(9) pm] is shorter than those of the
coordinated carbonyl groups in 2a, 3, and indigo itself. This
suggests that the inter- and intramolecular N - H...O bridging in free
has been disrupted. Crystals of 2 a con-
Verlagsgesel~.~chuJr
mbH, 0-6940 Weinheim, 1989
0570-OR33/89/i111-15298 02.SO/O
1529
Table 1. Selected bond lengths [pm] for indigo, 2 a . and 3
Indigo [6c]
~~
~
Pd-CI
Pd-P
Pd-N
Pd-0
Cl-C1'
CI-Nl
C1'-Nl'
CI'-C2'
CLC2
c2'-0 1'
c2-01
Fig. I . Molecular structure of 2a at 21 C in the crystal. 20% probability level.
P2,;n. a = 1248.5(4), h = 1372.1(3). c = 1691.7(5) pm. {i
= 98.87(2)'.
V = 2.X63(1) nm'. Z = 4, p ( M o K a )= 0.81 mm-', Wyckoff scan. Aw = 1.2
4 <6I
30'' min-I. 4 5 2 0 < 50 ; 9918 reflections measured. of which 5021
were unique and 4141 observed [I 2 2u(O], 257 parameters. Empirical absorption correction (Psi scan, using 10 reflections. 36 measurements each).
R = 0.075, R , = 0.079, w = [uL(F,)+ 0.0007 Fz1-I. Maximum ofresidual electron density 1.33 x
e pm-3. Hydrogen atoms in calculated positions. Programs used: SHELX 86. SHELX 76 and SHELXTL-Plus. [lo]
.
~~
2a
3
~~~-~~
~~~~~
230.9(2)
225.2(2)
21 1 .8(5)
203.8(5)
137.0(10)
135.4(9)
139.5(9)
144.8(9)
151 3(9)
127.6(8)
122.4(9)
I34.2(5)
138.2(6)
138.2(6)
145.9(5)
145.9(5)
124.0(5)
124.0(5 )
229.5(6)
224.9( 3)
213.X(9)
202.2(12)
134.4(22)
14I .8(22)
137.8(21)
147.8(21)
151.4(16)
132.2(21)
128.6(20)
of the two fivemembered rings about the central double
bond in the indigo anion also interferes with conditions that
are necessary for N-H...O bridging. The absence of such
bridges is apparent from IR spectra (Table 2). Thus, the
sharp vNH and vco bands of the non-coordinated carbonyl
groups in 1 and 2 a are shifted to higher wavenumbers relative to the corresponding bands of indigo.''"]
Table 2. IR data for indigo, octahydroindigo. and 1-3 in Nujol (i. [cm-'I).
Indigo
1, M = C u
2a
Octahydroindigo
3
rs(NH)
Y(C0). r(C = C)
3270 (br)
3398
3350
3340 (br)
1625, 1610, 1580
1680 [a], 1635. 1610, 1595. 1575
1675 [a]. 1650. 1610. 1595. 1575
1630. 1550. 1460, 1440, 1415
t635. 1570, 1455, 1415, 1395
[a] Non-coordinated C = O
Additional complexes of indigo and related systems will be
prepared in order to investigate their potential as energy
transfer agents or catalysts.
Experimentul Procedure
All work was conducted under nitrogen and in anhydrous solvents.
Fig. 2. Molecular structure of 3 at 21 'C in the crystal, 20% probability level.
Pi. u = 1274(1), h = 1384(1), c = 1489(1) pm, z = 63.85(7). fl = 77.42(7),
y = 82.07(8)", V = 2.297(4) nm3* Z = 2, p(MoKa)= 0.99 rnm-'. w scan.
A o = 1.4", 6 5 w s 30- min- ', 4 I
20 I
S O : 12 359 reflections measured. of
which were 7228 unique and 3696 observed [ I 2 2u(()J. 338 parameters. Empirical absorption correction (Psi scan, using 11 reflections, 36 measurements
each). R = 0.077, R, = 0.081. i ( ' = [a' (F,) + 0.0007 F 2 I - l . Maximum ofree pm-3. Hydrogen atoms incalculated posisidualelectron density 1.30 x
tions. The bond angles of the C atoms in one of the nBu,P ligands (high c'
values) were fixed. Programs used: SHELX 86. SHELX 76 and SHELXTLPlus. [lo]
tain pairs of coplanar molecules that are rotated relative to
each other by 180", thereby eliminating the possibility of
intermolecular N - H.. .O bridges. Apparently the twisting
1 570
(in VCH Vrrlugsgesellschufi mhH. 0-6940 Weinhcim,1989
2 a : A suspension of 24 mg (1 mmol) of NaH and 350 mg (1.33 mmol) of indigo
(Fluka) in 10 mL of T H F was heated for 15 min under reflux. After cooling the
green suspension, 380 mg (0.5 mmol) of [ClzPdPnBu,], was added. The reaction solution was stirred for 3 h at room temperature and then filtered (glass
frit, G4). Removal of the T H F in vacuo left a dark residue that was dissolved
in 5 mL of dichloromethane. This solution was filtered, and solvent was again
removed in vacuo. Za was obtained as a dark, granular material; yield 300 mg
(50%). Crystallization from dichloromethane/pentane. VIS spectroscopy
=
,748 nm, log i: = 4.0. "P N M R (109 MHz. CD,CI,):
(CHCI,): i,,
6 = 23.47.*HNMR(270MHz,CD,C12):b =0.99(1,9H), 1.52-1.93(m.l8H).
6.9 (q.2H). 7.18 (d.1 H), 7.37 (4,2H). 7.47 (d,l H). 7.58 (d.1 H). 8.46 (d.1 H).
9.07 (s,NH).
3: To a stirred suspension of 140 mg (0.5 mmol) of o~tahydroindigo'~'
and
168 mg ( 1 mmol) of silver acetate in l 0 m L of T H F were added 500mg
(0.66mmol) of (CI,PdPnBu,),. The reaction mixture was stirred for 12 h at
room temperature and filtered through a glass frit ((34). Solvent was removed
in vacuo. The residue was taken up in 15 mL of ether and again filtered Unreacted starting complex was precipitated by addition of 15 m L of pentane and
cooling to - 1 5 ~ C (3d). The cold solution was decanted and solvent was removed in vacuo. 3 was obtained as a dark green powder; yield 360 mg (75%).
VIS spectroscopy (CHCI,): i.,,=
, 663 nm, log c = 3.5. "P NMR (109 MHz,
CD'CI,): d: = 21.6. 'H N M R (90MHz. CD,CI,): h = 0.9 (t. 18H). 1.4-1.8
(m,44H), 2.1 (t,4H); 3.0 (t.4H).
Received: March 29, 1989 [Z 3251 IEJ
Publication was delayed at the authors' request
German version: Angen. Chem. 1Ut (1989) 1532
[I] a ) A . von Bdeyer. Eer. D/.Y/I. Chem. Ges. 33/31 (1900) supplement IV.
p. LI; b)R. Huisgen, Angeu. Chrm. 98 (1986) 297: Angrit.. Chcm. I n / . Ed.
Engl. 25 (1986) 297.
0570-0833iS9jllil-15~(~
$02.50/0
Angeir. Chem. Inr.
Ed. Engl. 2S (19S9J No. I 1
[2] K Kunr. Ber. Dtsch. Ch<,m.Grs. 55 (1922) 3688.
[3] K. Kuhn, H. Machemer, E r r . Dlsch. Chem. Ges. 61 (1928) 118; H.
Machemer, J. prukt. Chem. 127 (1930) 109.
[4] A compound isolated from the reaction of pentacarbonyliron and indigo,
reported to be extremely sensitive to oxygen (a property we have confirmed). was introduced as a "Breathing Model of Indigo Blue": K. Kunz,
A . J. KreO, Eer. Dtseh. Chem. Ges. 60 (1927) 367; W. Hieber, F. Sonnekalb,
iliiil. 61 (1928) 565. However, i t has been shown that 0, uptake by this
indigo-iron complex is irreversible: L. E Larkworthy, J. Chem. Sot. 1961.
4025. Khodium(iu) compounds of indigo carmine (5,5'-indigodisulfonic
acid disodium salt). which were not further characterized. catalyze the
hydroformylation of olefins: V. A. Avilov. E. G. Chepdikin, M. L.
Khidekel, In.. AXod. N a r k SSSR Ser. Khim. 1974. 2559; Chem. Ahsir. 82
(1975) 105 8OX. The thermal behavior of indigo carmine-transition metal
compounds has been investigated: J. M. Salas-Peregrin. J. Sudrez-Varela.
77iiwn. Arid. 29 (1984) 515.
[ 5 ] MO calculations (Dr. H . U . Wagner) are in progress. For MO calculations
on indigo cf. M. Klessinger. W. Luttke, Tetrahedron Suppl. -7 (1963) 315;
M Klessinger. Chem. Un.
[6] a ) A . Keis. W. Schneider, Z. Krrstullugr. Mineral. 68 (1928) 543: b)H. von
Eller. Bull. Snc. Chim. Fr. 106 (1Y55) 1426, c)for a recent, precise crystal
structure analysis of indigo (with localization of H atoms) see: P. Siisse. M.
Stein\. V. Kupcik, 2. Kristullogr. 184 (1988) 269.
[7] H. %'qek. U. Nagel, W. Beck, Chem. Brr. I21 (1988) 1021.
[8] a)W. Luttke. M. Klessinger. Chem. Eer. 97(1964)2342; M. Klessinger. W.
Luttkc. ibrd. YY (1966) 2136; b)H. Meier. W. Luttke. Liehigs Ann. Chem.
19HI. 1303.
[Y] G . Pfeiffer. H. Bauer. Justus Liehigs Ann. Cliem. 1976. 383; Liehig.c Ann.
Chem. 1980. 564.
[lo] Further details of the crystal structure investigation are available on requeht from the Fachinformationszentrum Karlsruhe, GeSelkhdft fur wis-
senschaftlich-technische Information mbH, D-7514 Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository number CSD-53930, the
names of the authors. and the journal citation.
Stack-Type Redox Systems: Synthesis
via Repeated Carbanion Alkylation and
Electron Transfer Studies **
By Jiirgen Almander, Marianne Ehrenfreund, Jiirgen Fiedler,
Walter Hubrr,* Hans-Joachim Rader, and Klaus Miillen *
Dedicated to Projkssor Wolfgang Liittke on the occasion
of Itis 70th birthday
Stack-type x-systems such as multiply layered phanes". 21
o r radical cation saltsL3]can be used as models for studying
one-dimensional charge transport.141We recently reported
the preparation of 3a and 3b, members of a new class of
two-layer n - ~ y s t e m s [ ~in" ~which the disk-shaped subunits
are bridged [14]-annulenes; in contrast to the phanes, the
subunits are linked by bridging groups "within" the x-system, and the distance between the layers can readily be varied. We have now been able to synthesize multiply layered
homologues of 3 with up to five single layers by means of a
"one-pot" reaction in which the pyrene isomer 1 1sb*6-71 undergoes reductive alkylation. The multilayer redox systems
are constructed from separate electroactive groups and can
be subjected to successive electron transfer reactions.ls'-el
[*] Prof. Dr. K. Miillen. DipLChem. J. Alexander, Dr. J. Fiedler,
DipLChem. H.-J. Kdder
Institut fur Organische Chemie der Universitit
J.-J.-Becher-Weg 18-22, D-6500 Mainz 1 (FKG)
Priv.-Doz Dr. W. Huber [+I, DipLChem. M. Ehrenfreund
Institut fur Physikalische Chemie der Universitit
Klingelbcrgstrasse 80. CH-4056 Basel (Switzerland)
['I
Present address:
Hoffmann-La Roche& Co AG, CH-4002 Basel (Switzerbdnd)
[**I
Reductive iransformailons. Part 13. This work was supported by the
Deutsche Forschungsgerneinschaft and the Fonds der Chemischen Industrie. Part 12. 0 . Bender, M. Przybylski, K. Mullen. Mukromol. Chern.. in
press.
AnRew. Chem. Int. Ed. B i g / . 28 (198Y) No. I 1
$3
The energies of interaction between the charged subunits and
the nature of the charge distribution are important for the
redox steps formed, and have been determined by cyclovoltammetry and ESR spectroscopy, respectively.
The synthesis of the two-layer compound 3 is made possible by the fact that 1 can be alkylated in a regioselective
manner at the two central carbon atoms via the dilithium salt
2.[5d.61
It is thus, for example, possible to obtain the nucleophile 4a and the electrophile 5a; these can then undergo
coupling to give 3a in 9 5 % yieldI5"I (see Scheme 1,
route
Analogues with more than two layers should be available
from a reaction in which the bifunctional nucleophile 2
(= l Z 0 / 2Li@)is treated with bifunctional electrophiles such
as 6; the resulting monoalkylation products 7 are both elecXRX'
6 a : X=X'=CI, R=(CH,),
6b: X=CI(Br), X=OSO,CF,, R=(CH,),
6 ~X=X'=OSO,CH,,
:
R=(CH,),
6 d . X = X =OSO,CH,, R=(CH,),C C(CH,),
6e: X=X'=OSO,CH,, R=(CHZ)h
tro- and nucleophilic and can in principle form stack-type
compounds in a polyreaction. If, however, 2 is treated with
1,3-dichloropropane 6a, the intermediate 7 a (X = C1) reacts
mainly via intramolecular cyclisation to give 8. Stack-type
molecules are not formed, and the expected diadduct 9a is
also only formed as a by-product, even if an excess of the
alkylating agent is used (molar ratio 8:9a = 5:3).16] The
bifunctional electrophile 9a is, however, formed in 70 YO
yield when l-chloro/bromo-3-(trifluoromethylsulfonyloxy)propane 6b is used, since in this case 2 reacts only with the
more reactive electrophilic group.
The intramolecular cyclization of 7 to 8 can be prevented
by variation of the alkylating agent; while the use of 6d with
a hex-3-ynediyl unit naturally prevents cyclization, the
analogous hexanediyl (6e) and even the butanediyl (6c)
agents also show no tendency to cyclization. When 6c is
allowed to react with 2.5 equivalents of 2, followed by a
trapping reaction with the monofunctional electrophile
dimethyl sulfate, the double layer compounds 3b-d are obtained in 32, 50 and 5 0 % yield, respectively (after chromatography and recrystallization). The intermediates 7 b-d
apparently react preferentially with 2 to form the dianions
10 b-d, which then undergo double methylation. Compounds 3 can thus be readily obtained via two routes (1,II).
It is significant that the "triple-decker" compounds 1 1 c
and 11 dr8]are formed as by-products of the formation of the
new systems 3c and 3d in yields of ca. 10%. This makes it
certain that the dianions 1Oc and 1Od can undergo further
alkylation by 6d o r 6e prior to the termination reaction with
dimethyl sulfate (route 111). The short-chain system lob, in
contrast, is precipitated from the solution and thus cannot
undergo further reactions.
We expect that the triply o r multiply layered products will
be formed in preference to the double layers 3 if a molar ratio
of 2 to 6c-e of 1 :1 rather than 2.5: 1 is used; in this case the
nucleophilic positions of 10 will be alkylated by 6, so that the
alkylation sequence is continued. The reaction of 2 and 6e
(1 : 1, THF, 20 "C, 24 h) does indeed give a mixture of soluble
oligomers in 70% yield (loo/, of 3d are also formed); mass
spectrometry indicates the mixture to contain the three, fourand five-layer systems 11d, 12 and 13 which can be distinguished by 'H NMR spectroscopy (routes 111. IV).
It would be particularly attractive for studies of electron
hopping processes between the annulene units in 3 and 1 1 to
VCH Verlugsgesellschafi mhH. 0-6940 Weinhelm. 1989
o57o-0833j8YjJtJl-1531
S 02.SOjO
1531
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indigo, compounds, mono, complexes, ligand, structure, synthesis, containing, pdii, metali, ptii, anion, bis, chelate, octahydroindigo
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