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Hydrolysis to a Complex with a Central Octahedral (6-O)In6 Unit.

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in which one P atom is replaced by an S atom, and one edge
consists o f a Mn(CO),-PMe,-P unit. The structuralparameters of the cubane section are similar to those of the parent
c o m p o ~ n d .The
~ ~ phosphorus
~~I
atom P4 is shifted from the
ideal cubic position because of the PMe, bridge (the interplanar angle between C 1 1-P3-C 1l a and C 1 1-P4-C 1 l a is
147.7"). The P2-P4 distance is somewhat shorter than that
of a single bond.
If reactions, in which the steric demand of the R group is
between methyl and cyclohexyl, for example R = Ph, are
carried out starting from 1, in addition to 3 and the corresponding pentacycle 4 with Ph instead of Me, the metal-free,
intense yellow bicyclic compound 5 is obtained (Table 1).
[9] E. Lindner, R. Fawzl. H. A. Mayer, K. Eichele, K. Pohmer, fnorg. Chem.
1991.30, 1102-1107.
[lo] Crystal structure analysis (Sieinens-P4 diffractometer): 4crystallized from
n-hexane, C,,,H,,MnO,P,S,
M = 532.3, crystal dimensions 0.2 x 0.5 x
0.5 mm', orthorhombic. space group Pnmu (Pna2, was checked), n =
984.7(2), h = 1463.6(3), c = 1744.6(3) pm, V = 2514.3(8) x 10' pm', pcAlCd
= 1.406 gem-', 2 = 4 (measurement temperature 173 K), Mo,, radiation
( p = 0.881 mm-'), 28 = 4-45', total number of reflections 12462, number of symmetry-independent reflections with I 2 2a(l) 1623, refined
parameters 160. absorption correction Y scan, R = 0.022. R, = 0.026.
S = 0.94, residual electron density 0.23 e k ' . solution and refinement
with the SHELXTL-PC program. The positions of S l j P l and Pla/Sla
were each refined with the occupation factor 0.5. The H atoms were geometrically positioned (riding model). Further details of the crystal structure investigation may he obtained from the Fachinformationszentrum
Karlsruhe. Gesellschaft fur wissenschaftlich-technische Information mbH,
D-76344 Eggenstein-Leopoldshafen (FRG) on quoting the depository
number CSD-57347, the names of the authors, and the journal citation.
R'
Hydrolysis to a Complex with a Central,
Octahedral (p6-O)In6 Unit**
The described reaction can also be transferred to other
phosphaalkynes such as adamantyl- and methylcyclohexylphosphaacetylenes (a3'P of 3, R' = adamantyl (in dimeth= 48.7 Hz; of 3 , R =
oxyethane): 245.04 and 256.24,2Jp,p
MeC,H,, (in C,D,): 255.26 and 265.16, zJp,p
= 49.7Hz).
Experimental Procedure
By Kaspar Hegetschweiler,* Michele Ghisletta,
Thomas E Fassler, and Reinhard Nesper
In a number of studies over the last two years we have been
able to show that the ligand 1,3,5-triamino-I ,3,5-trideoxycis-inositol (taci) is remarkably versatile in complexing metal
ions."
In aqueous solution monovalent to tetravaient
cations of the groups 1 15 are readily complexed. Two different chair conformations (Scheme 1) enable the binding of
a metal ion to three nitrogen atoms (a), two nitrogen atoms
and one oxygen atom (b), two oxygen atoms and one nitrogen atom (c) as well as three oxygen atoms (d). In the
[M(taci),13+ complexes (M = Al, Ga, TI), coordination proceeds by binding the cations at the triaxial sites (a) or (d). The
oxophilic A13 is coordinated exclusively by oxygen donors,
whereas T13+shows an N, coordination sphere. Ga3+lies in
between A13+ and TI3+and consequently is bound to three
nitrogen atoms of one ligand and to three oxygen atoms of
the
In contrast, P b 2 + and Bi3+ prefer the asymmetric coordination mode (c).I41
-4J
3: A solution of 1 a (535 mg, 1.35 mmol) and 2 (340 mg, 3.40 mmol) was heated
to 66 - C for 5 h in T H F (50 mL). After the removal of the solvent at 50 mbar
the residue was taken up in petroleum ether 60190 (20 mL) and purified on a
short silica gel column. The main product was separated by MPLC with
petroleum ether 60190 on a silica gel column. First fraction: 3 (122 mg, 78%
yield based o n 0.675 mmol la). correct elemental analysis, m.p. 10°C; third
(310 mg, 81 % based on
fraction: [(OC),(HPCy2)Mn($-PCy2=S)]
0.675 mmol 1 a; H stems from traces of moisture). yellow powder. correct
elemental analysis, m.p. 123 ' C .
~
+
4: 1 b (470 mg. 0.90 mmol, exists as dimer [6c]) and 2 (640 mg, 6.40 mmol) in
T H F (50 mL) were mixed together and heated under reflux for 22 h. The
workup was carried out as for 3 but with petroleum ether/ethyI acetate 311 as
eluent. Third fraction. 4 (420 mg, 44%), orange single crystals from n-hexane,
correct elemental analysis. m.p. 210 "C.
5: 1. R = Ph. (263 mg, 0.34 mmol) was heated with 2 (200 mg, 2.00 mmol) in
T H F (40 mL) to 50 ;C for 44 h. After the removal of the solvent under vacuum.
the residue was taken up in petroleum etherjethyl acetate (1011) (20 mL). titered (P4). and separated on a silica gel column with the same eluent. First
fraction: 5 (12.4 mg, 11 %) yellow solid.
For the assignment of the "P and "C N M R signals, 3.4, and 5 were synthesized with "C-labeled 2.
Received: June 2. 1993 [Z6116IE]
German version: Angen.. Chern. 1993, 10s. 1521
[I] M. Regitz in Orgunic Synrhesr.r via Orgunomr/ollics(Eds.: D. Enders. H.-J.
Gals. W. Keim), Vieweg. Braunschweig, 1993, p. 93, and references
therein .
[21 P. Binger, T Wettling, R. Schneider, F. Zurmuhlen, U. Bergstrisser, J.
Hoffmann, G. Maas. M. Regitz, Angew. Chrm. 1991. 103, 208-211;
Angrw. Chpm. Int. Ed. Engl. 1991. 30, 207-210.
[3] M. Birkel, J. Schulz, U . Bergstrlsser, M. Regitz, Angers. Cheni.1992, 104,
870-873; Angeic. Cham. Int. Ed. Engt. 1992, 31, 879-882.
141 T. Wettling. J. Schneider, 0. Wagner. C. G. Ki-eiter, M. Regitz, Angeir.
Chem. 1989. 101, 1035-1037; Angers. Chem. In/. Ed. EngI. 1989,28.10131014.
[5] B. Breit, U. Bergstrisser. G . Maas, M. Regitz. Angeir. Chem. 1992. 104.
1043-1046; Anger$.. Chem. In!. Ed. Engl. 1992,31, 1055-1058.
[6] a) E. Lindner, Ads. Heterocycl. Chrm. 1986. 39. 237-279; b) E. Lindner.
V. Kiss, W. Hiller, R. Fawzi, Anyew. Chem. 1989, 101. 460-462; Angeu.
Cham. Inr. Ed. Engl. 1989, 2X. 448-450; c)E. Lindner, V. Kiss. H. A.
Mayer, Chrn?. Em-. 1990, 123. 783-790; d) E. Lindner, T. Schlenker. R.
Fawzi. C. Maichle. J. Organomer. Chem. 1993, in press.
[7] E. Lindner. A. Nothdurft, R. Fawzi. C. Maichle, J. Orgunoinet. Chem.
1992, 435. 213-224.
[XI A Schmidpeter. K. Karaghiosoff in Multiple Bonds und LOWCoordinution
in Phosphorous Chemistr~.,1. edition, (Eds.: M. Regitz, 0. J. Scherer)
Thieme, Stuttgart. 1990, p. 279. and references therein.
1426
t" VCH Verluysyesi~llschaftmhH, 0-694.51 W e m h m i , 1993
Scheme 1. Possible coordination modes of the ligand taci.
The stability constants determined in aqueous solution
show that the Al, Ga, and TI complexes are not stable with
respect to the formation of solid hydroxides or oxides.[31Indeed, the tendency to hydrolyze was confirmed by spectro[*] Dr. K . Hegetschweiler, Dip].-Chem. M. Ghisletta. Dr. T. F. Fissler.
Prof. R. Nesper
Laboratorium fur Anorganische Chemie
ETH Zentrum. CH-8092 Zurich (Switzerland)
TelefaX: Int. code (1)252-8935
[**I 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol,
a new, ligand with a remarkable versatility for metal ions, part 6. This work was supported by the ETH
Zurich. Part 5: K. Hegetschweiler, R. D. Hancock. M. Ghisletta, T. Kradolfer. V. Gramlich, H. W. Schmalle, Inorx. Chem.. in press.
+
OS70-0833/93/10II)-142t,$10.00+ ,2510
Angeu. Chem. Int. Ed. Engl. 1993, 32, No. 10
scopic and potentiometric measurements. These measurements clearly show that the rate of hydrolysis increases dramatically in the sequence Al"' < Ga"' < TI"'. Starting from
the corresponding In"' complex we could isolate a hydrolysis
product of the composition [OIn,(taci-3 H),](NO,),
-8H z O from aqueous solution. Spectroscopic methodsL5* as
well as an X-ray structural analysis['] were used for its characterization.
Discrete [OIn,(taci-3 H),I4+ ions, whose structure is
shown in Figure 1, are found in the crystal. A single oxide ion
in the center of the complex is surrounded by six In"' ions.r81
Fig. 1. Structure of [OIn,(taci-3 H)J4+. [In3(taci-3H)] fragment (top left).
In,O,, core (top right). and perspective overall view (bottom). The vibrational
ellipsoids correspond to the 50% probability level. Bond lengths [pm]: In-O,,,
241.7(5) ~264.3(6).In-O,aL,213.0(5)-220.8(5), In-N 232.3(6)-236.0(5), C - 0
141.7(6) 143.7(7). C-N 145.5(8)-147.5(6), C-C 151.2(6)-154.3(8). Selected
angles [ 1: 0 - I n - 0 (intraligdnd) 85.1(2)-87.0(1), 0 - I n - 0 (interligand. cis)
89.2(1) -90.7(2), 0 - I n - 0 (interligand, trans) 154.5(2)- 161.5(5), 0-In-O,,,
76.7(2)k81.0(1). 0-In-N (intrahgand) 71.5(2)-75.4(2), 0-In-N (interligand)
12?.3(3)-129.0(1). N-In-O,,, 141.4(2)- 144.1(1), N-In-N 73.0(2)-76.4(3), InO,,,-In ( c k ) 88.6(1)-90.4(1). In-O,,,-In ((runs) 177.2(2)- 180.0, C-0-In
113.4(.3) 11 5 614). C-N-In 97.3(3)-98.8(4).
~
This OIn, unit is in turn encapsulated by four triply deprotonated taci molecules. All six donor atoms of each ligand
molecule interact with the In"' ions with the hydroxyl groups
deprotonated. In contrast to the terminally coordinating
amino groups, these deprotonated hydroxyl groups bridge
two In"' ions. Each ligand molecule binds three In"' ions, and
every In"' ion is simultaneously coordinated by two ligand
molecules, so that all six In"' ions obtain the coordination
number 7. The In-Ooxo bonds are unusually long. However,
the other In-0 and In-N bond lengths agree well with
those values found in other complexes with a sevenfold coordinated In"'.r91 The twelve coordinating alkoxo groups,
together with the six In"' ions and the central oxide ion, form
an In,Ol, core with approximate 0, symmetry.
The crystallographic symmetry of the entire complex is
C , . However, N M R spectroscopic measurements reveal that
the complex has tetrahedral T, symmetry in solution: the
observation of only two signals in the ' H N M R and 13C
N M R spectra, respectively, demonstrate the equivalence of
the four ligands as well as that of the three 0 and the three
N substituted C H groups within a ligand. Four C , axes thus
pass through the central oxygen atom and the center of the
cyclohexane rings, whilst the three S, axes correspond to the
space diagonals in the OIn, octahedron. It is noteworthy
that [OIn,(taci),-xH] units are also preserved in the mass
spectrometer. Signals due to single monopositive ions, which
are generated by multiple deprotonation and by association
of NO;, are observed.["
The reaction of taci with TI"' in the ratio of 2: 1 in methanol
gave the mononuclear complex ion [Tl(taci)J3 +.L31 The
analogous reaction with In'" gives a crude product which
contains the mononuclear ion [1n(taci),l3' as main component according to mass spectrometry and N M R spectroscopy.
[OIn,(taci-3 H),I4+ is formed subsequently in aqueous solution and can be regarded as a first intermediate in the
hydrolytic polymerization of a mononuclear precursor complex. However, in the thermodynamically stable In,O, , the
final product of this polymerization, the oxygen atoms are
four- and not six-coordinate.[l9]
Polynuclear metal complexes with a central OM, unit are
well known." - 1 3 ] In the isopoly anions of V", Nb", Ta",
Mo", and W"', this unit is obtained by the linking of MO,
octahedra over common edges, resulting in the formation
of the characteristic M 6 0 i , core.['21 Related structures have
recently also been found for complexes of V'", Mn"/Mn"',
and Fe"'. However, in these complexes, the peripheral 0x0
ligands are replaced by alkoxo groups.[131To date, the
M,O,, core described here has only been known for transition metals. [OTn,(taci-3 H),],' is the first main group element complex of this type. Moreover, it differs from the
previously known complexes by adopting the coordination
number 7 at the metal.
The formation of complexes with a M,Ol, core can be
understood as a spontaneous self association of a mononuclear precursor complex. It is noteworthy that this core is
observed in [OIn,(taci-3 H),],',
[OFe,(OCH,)l,]2-, and
[ M O , O ~ ~ ] that
~ - , is metal ions with distinctly different
chemical properties. We therefore assume that the M,O,,
unit, due to its particularly favorable geometry, is a common
structural element in oligonuclear hydrolysis products of
metal complexes with a relatively small number of metal
centers.
Experimental Procedure
A solution of indium(ii1) nitrate (0.42 g. 1.4 mmol) in methanol (20 mL) was
added dropwise with stirring to a solution of taci (0.51 g. 2.88 mmol) in
methanol (20 mL). A white solid precipitated immediately. The suspension was
stirred for an additional hour at room temperature and the solid was then
filtered off. This residue was dissolved in water (10 mL), filtered through Celite
and the colorless filtrate was layered with ethanol. After a few days colorless
crystals were formed which were suitable for single-crystal X-ray analysis.
Received: May 21. 1993 [Z60971E]
German version: A n p i . . Cliem. 1993. 105. 1514
~~
[I] H. W. Schmalle, K. Hegetschweiler, M . Ghisletta, A i m Crysiolhgr. Swr.
C 1991, 47, 2047-2052.
[21 K. Hegetschweiler, V. Gramlich, M. Ghisletta. H. Samaras. Inorg. Clwn.
1992.31.2341 -2346.
131 K. Hegetschweiler. M. Ghisletta, T. F. Fissler. R. Nesper, H. W. Schmalle,
G. Rihs, Inorg. Clwm. 1993, 32. 2032-2041
[4] K. Hegetschweiler, M. Ghisletta. V. Gramlich, lnorR C'hrr?i 1993. 32.
2699- 2704.
[Sl ' H N M R (200 MHz, D,O): S = 4.00 (t, J = 3.2 Hz, 12H). 3.17 (t,
J = 3.2 Hz. 12H); I 3 C N M R (50.4 MHz, D,O. TSP): d =74.3, 53.0.
[61 FAB' mass spectra were recorded on a double focussing VG-ZAB-VSEQ
mass spectrometer. The aqueous sample solution was mixed with a glycerol matrix. Assignments in the range 1000<m/;< 1500; 1398.6 (100%)
[[OIn,(taci),]-l5 HI'. 1461.6 (36) [[OIn,(taci),](NO,)-14H] * I 1524.8
(12) [[OIn,(taci),](NO,),-13 HI ',
[71 The composition C,,H,,In,N,,O,,~8H,O
was confirmed by C . H, N
analyses. The compound crystallized in the monoclinic space group C2ir.
(no 15) with u=2130(3), h=1251(2), c=2295(3)pm, 8=325.28(9)’.
Z = 4, V = 4992(12) x lo6 pm’, Mo,, radiation, graphite monochromator, four-circle diffractometer STOE STADI4. reflections: 6474 observed.
6322 unique. of these 5141 with 1 > 2 . 5 0 ( / ) were used for the refinement of
358 parameters: structure solution by using direct methods. no absorption
correction. R = 0.0328, Rw = 0.0409, residual electron density + 0.99 1
- 1.2 eo/A’. Further details ofthe crystal structure investigation are available on request from the Director of the Cambridge Crystallographic Data
Centre, 12 Union Road, GB-Cambridge CB2 1EZ (UK). on quoting the
full journal citation.
[XI We exclude the possibility of O H - instead of 0’- being in the center for
the following reasons: 1) The resulting divergence of the charge balance
0 2 -+ 6 1 n 3 + + 4(taci-3H)’- + 4NO; would require compensation
by either a lower oxidation state for one In atom. by an additional deprotonation of a Iigand. or by the occupation of a noncoordinated H,O
position by O H - . However, the N M R spectroscopic evidence of four
symmetry-equivalent ligands, the I n - 0 and In-N distances. and the observation that the aqueous complex solution showed almost no alkaline
reaction are all not in agreement with such compensations. 2) A disordered
hydroxide ion in the center of the approximately octahedral complex
should result in an increased temperature factor. This also is not observed.
191 A. Riesen. T.A. Kadeii. W. Ritter, H. R Miicke. J Chmi. Soc. Chmnr.
Cuniniun. 1989, 460-462.
[lo] M . Marezio. Actu Cr~stullogr.1966, 20. 723-728.
[I I ] a) P. Miele. J. D. Foulon. N. Hovnanian, L. Cot. J. Chem. Soc. Chem.
Comniun. 1993. 29-31; b) K. G. Caulton. M . H. Chisholm, S. R. Drake,
J. C Huffman, h d 1990. 1 4 9 8 ~1499: c ) R. Schmid. A. Mosset. J. Galy.
Inorg. Chini. Actu 1991, 179. 167-170.
1121 Q. Chen, J. Zubieta, Coorrl. Cheni. Rris. 1992, 114. 107-167.
1131 a) M. I. Khan. Q. Chen. D . P. Goshorn, J. Zubieta. Inorg. Cheni. 1993,32.
672-680; b) M. Cavaluzzo, Q. Chen. J. Zuhieta, J. Cl7em. SOC.Chcm.
Cummun. 1993. 131 - 1 3 3 ; ~ )K . Hegetschweiler, H.Schmalle, H. M. Streit.
W. Schneider. Inurg. Chum. 1990. 29. 3625-3627: d) K. Hegetschweiler.
H. W. Schmalle, H . M. Streit. V. Gramlich. H.-U. Hund. I. Erni. ihid. 1992.
31. 1299-1302.
[AltBu]; : EPR Spectroscopic Evidence
and Ab Initio Calculations**
Perhalogenated cfoso-borates [BX],’- (X = CI, Br, I) with
n = 8- 12[’-31have been known for some time.[41Recently,
the first analogous aluminum compound, [AliBu]?; ,Is1 was
characterized. We report here on the second anionic aluminum cluster, the radical anion [AlrBu], 1’-.16] After tetrahedral [(AICP*)~]‘~*and icosahedral [AliBu]:; ,I5]1’- is
the first aluminum cluster derived from octahedral symmetry.
The reaction of a solution of AlCl in toluene and diethyl
ether’”] with tBuLi gave a dark red solution from which
LiCl slowly precipitated.“ ‘I A homogeneous reaction pathway is revealed by N M R spectroscopy.1121The analysis of
[‘*I
Prof. Dr. H. Schnockel>+]Dip].-Chem. C Dohmeier.
Dipl. Chem. M. Mocker
Institut fur Anorganische Chemie der Universitit
Meiserstrasse I , D-80333 Miinchen (FRG)
New address: Institut fur Anorganische Chemie der Universitdt
Postfach 6980, D-76128 Karlsruhe (FRG)
Telefax: Int. code + (721)608-4290
Priv.-Doz. Dr. A. Lotr
Institut fur Phystkalische Cheinie der Universitat Miinchen (FRG)
Prof. Dr. Ahlrichs. Dipl. Chem. U. Schneider
Lehrstuhl fur Theoretische Chemie
Institut fur Physikalische Chemie und Elektrochemie der Universitit
Kaiserstrasse 12. D-76128 Karlsruhe (FRG)
This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie. We thank Prof. Dr. J. Voitldnder for
providing the EPR spectroineter
1428
’(>
VC‘H ~ r / r i g . ~ g ~ ~ . ~mhH.
e l / . ~D-6945/
~ / z u ~ Weinheim, 1993
Fig. I . EPR spectrum of [AlrBu]; in C,D, (u(”A1)
=
8.2 G, g
=
2.008)
clearly point to a compound with six equivalent aluminurn
atoms (”AI: loo%, I = 5/2). The analogous alkylation of
AIBr[’41instead of AICI, gives, without reduction, a product
with the same N M R and EPR spectra.[”I The compound,
evidenced by EPR, thus cannot be a species containing halogen. Since neither isomerization nor elimination of the tBu
substituents are observed, the conclusion is that the radical
anion [AltBu], (l‘-) must be present. The isolation of
[(AIfBu),] (1) and M,’l’- [Eq. (a)] has so far not been successful.“ 61
rBuLi
-
Dedicated to Professor Hans Bock
on the occasion of his 65th birthday
[‘I
t
3297 G
6A1C1
By Carsten Dohmeier, Mario Mocker,
Hansgeorg Schnockel,* Albert Lotz, Uwe Schneider,
and Reinhart Ahlrichs*
[*I
the product shows it to be a monovalent aluminum comIf the solution is reduced with Na/K alloy, hardly
any differences in the N M R spectra can be detected. Only
the proton spectrum indicates the presence of a paramagnetic species by showing a very broad resonance (6 = 1.4). This
was confirmed by the EPR spectrum (Fig. 1). The 31 lines
LiCl
“[(AltBu),]”
Na,K
M:[Al/Bu],
(a)
In order to elucidate the structure and electron distribution of l ’ - , a quantum chemical geometry ~ p t i m i z a t i o n [ ” ~
was carried out at the S C F level. In addition, AltBu and 1
were also studied with these methods.
Wade’s rules predict a perfectly regular octahedron for Al,
cages only for the dianion. For neutral compounds o r monoanions, however, an octahedral cage leads to the occupation
of the t,, HOMO with four or five electrons, respectively,
and thus to a Jahn-Teller distortion, which was verified in the
SCF approximation. All calculations were carried out in D,,
symmetry (Fig. 2), since this is the highest possible symmetry
consistent with tBu groups as ligands, leads to six equivalent
Al atoms, and, moreover, allows a continuous transition
between octahedron and ring.[’81 Then, from the t,, HOMO
Fig. 2. Ball-and-stick model of the structure of [AItBu]; (D3., symmetry) as
calculated with a b initio methods.
0S70-o833!93jln10-/42~$10,00+ .2SjO
Anggen.. Chem. In [ . Ed. Engl. 1993, 32, No. 10
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