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The First УAdamantoidФ Alkaline Earth Metal Chelate Complex Synthesis Structure and Reactivity.

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b
Fig. I . Crystal structure of 3 (hydrogen atoms omitted). Important bond
lengths [prn]: V-N(I) 167.9(5), V-N(2) 166.0(5), V - 0 173.5(5), V-CI 221.4(2),
P-N(I) 161.8(5), P-N(2) 162.1(5), 0-Si 162.5(5). Bond angles ["I in the central eight-membered ring at V 110.8(3), N 158.4(3), P 116.9(3). The molecule
possesses a crystallographic inversion center.
bonds are ca. 5-15 pm shorter than those in [S2N3VC12],,[61
but closely resemble those in open-chain systems.[']
The P-N bond lengths, on the other hand, lie in the
same range as those of similar cyclophosphazene systems.".'I The angles at the nitrogen atoms are about 10"
greater than those in P4N4Fsrthe only planar eight-membered phosphazene ring thus far reported in the literature.[')
I n mass spectroscopic investigations of 3, the molecular
ion could not be observed. The 'H-decoupled N M R spectra show singlets in the expected regions with extremely
large half-widths, which change very little even on lowering the temperature and which cannot be attributed to paramagnetism.['"'
finally treated with a little CH3CN. Large, brick-red rhombs of 3 crystallized out at -30°C. M.p. 206°C (decomp.), yield 3.1 g (SOu/'). IR:
V=l580 w, I430 s, 1248 m, 1187 vs, 1157 m, I l l 0 vs, 1065 sh, 1022 m,
995 rn, 901 vs, 845 sh, 836 vs, 748 m, 726 s, 704 sh, 680 s, 662 sh, 533 s
cm - '_
M. Witt, unpublished; in analogy t o Ph2P(NSiMe,)NHSiMeJ ( K . L. Paciorek, R. H. Kratzer, J . Org. Chem. 31 (1966) 2426). 2 was first described by w.Wolfs6erger a n d H Hager (2. Anorg Allg. Chem. 425
(1976) 169).
H. Noth, G. Meinel, 2. Anorg. Al/g Chem. 349 (1967) 225.
Crystal structure analysis of 3 : space group Pbca, a = l162.0(l),
b=1690.4(2), c=2011.3(8)pm, V=3.9507nm', Z = 4 , p = 0 . 7 m m - '
(Mo~,.); 4069 measured intensities, 2&,, =45". empirical absorption
correction, 2499 observed reflections with F>4o(F') used for the structure solution (Patterson and Fourier methods) and refinement, non-hydrogen atoms anisotropically, H atoms (partly located by difference
electron density determination) refined with a riding model, R = 0.067
(R,, =0.073, w - ' = a 2 ( F ) + 0 . 0 0 0 5 F 2 ) . Further details of the crystal structure investigation are available on request from the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D-75 14 Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository number CSD-52826, the
names of the authors, and the journal citation.
H. W. Roesky, J. Anhaus, H. G. Schmidt, G. M. Sheldrick, M. Noltemever. J . Chem. SOC.Dalton Trans. 1983. 1207.
[7j For a review of the bonding and bond order of transition metal-nitrogen
compounds see: K. Dehnicke, J . Strahle, Angew. Chem. 93 (1981) 451:
Angew. Chem. Int. Ed. Engl. 20 (1981) 413.
[8] H. R. Allcock: Phosphoru-Nitrogen Compounds, Academic Press, New
York 1972.
[9] H. McD. McGeachin, F. R. Tromans, J . Chem. Sot. 1961. 4777.
[lo] 29Si-NMR: 6=24.0 (A1,2=30 Hz); "P-NMR: 6 = - 12.6 ( A , , ? = 1000
Hz): "V-NMR: 6= -394.7 (An,,,=500 Hz). The lock (CDCI,) signal is
sharp. According to ESR studies (Dr. D. Marsh, MPI, Biophysikalische
Chemie, Gottingen), there are no unpaired electrons in the solid state.
[ I I] E. Schweda, K. D. Scherfise, K. Dehnicke, Z. Anorg. Allg. Chem 528
(1985) 117.
[I21 The synthesis and characterization of 4 will be reported elsewhere.
The First "Adamantoid"
Alkaline Earth Metal Chelate Complex:
Synthesis, Structure, and Reactivity**
By Rolf W. Saalfrank,* Armin Stark, Karl Peters, and
Hans Georg von Schnering"
Similar effects are observed in the case of 4, which is
accessible from [CI,VNSiMe,]["~ and Me3SiN=PPh2CI. 4
cannot be obtained by reaction of 3 with SOCI, or
PC 15.[1 l]
Received: November 16, 1987:
revised: December 23, 1987 [Z 2501 IE]
German version: Angew. Chem. 100 (1988) 852
Publication delayed at authors' request
CAS Registry numbers:
2, 61500-31-0; 3, 114490-50-5; 4, 114490-51-6: CIIVNSiMe3, 99589-88-5;
Ph:PN(SiMe&.
13685-61-5; Me,SiN=PPh2CI, 90413-89-1; Me,SiN1,
4648-54-8
[I] H. W. Roesky, K. V. Katti, U. Seseke, M. Witt, E. Egert, R. Herbst, G.
M. Sheldrick, Angew. Chem. 98 (1986) 447; Angew. Chem. Int. Ed. Engl.
25 (1986) 477; H. W. Roesky, K. V. Katti, U. Seseke, H. G. Schmidt, E.
Egen, R. Herbst, G. M. Sheldrick, J . Chem. Soc. Dalton Trans. 1987.
847: K. V. Katti, H. W. Roesky, M. Rietzel, Inorg. Chem. 26 (1987)
814.
121 Procedure for 3: A solution of I (1.7 g, 10 mmol) in C H 3 C N (20 mL)
was added dropwise under N2 to a solution of 2 (4.3 g, 10 mmol), prepared by oxidation 131 of Ph2PN(SiMe,), 141 with Me3SiN3, in CH,CN
(100 rnL). After 24 hours' stirring, the orange-red precipitate was filtered
off, washed with a small amount of CH,CN, dissolved in CH2C12,a n d
Angen. Chem Int. Ed. Engl. 27 (1988) No. 6
n,n-Dilithioalkanes are of special interest both from the
theoretical point of view and because of their remarkable
synthetic potentiaL1'] The same holds true for l,l-dilithioallyl phenyl sulfone,121dilithio(phenylsulfonyl)(trimethyl~ilyl)methane,[~'
and dilithio(tosy1)methyl iso~yanide.[~]
To our knowledge dilithiomalonate esters have so far
never been the subject of a concrete study. The C,C-dialkylation o r C,O-diacylation of malonic esters proceeds in
two steps via the malonic ester monoanion.['I
The synthon strategy has proven to be best for the development of new synthetic methods.l6] In this connection we
have paid special attention to tetradonor-substituted allenes l , which formally react like I,l-/1,3-dianions 2 of
malonic ester ( R ' = R2 = OEt) or malonic amides
(R' = RZ= NR,)."' I n extension of the concept developed
for the allenes 1 we have also used silyl enol ethers 3 of
1,3-dicarbonyl compounds as 1,3-dianion equivalents 2
(R', R2 = OEt, aryl).I8l
[*] Prof. Dr. R. W. Saalfrank, Dip1:Chem. A. Stark
Institut fur Organische Chemie der Universitat
Erlangen-Nurnberg
Henkestrasse 42, D-8520 Erlangen (FRG)
Prof. Dr. H. G . von Schnering, Dr. K. Peters
Max-Planck-lnstitut fur Festkorperforschung
Heisenbergstrasse 1, D-7000 Stuttgart 80 (FRG)
[**I "Adamantoid" Chelate Complexes. Part I. This work was supported by
the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen
Industrie.
0 VCH Verlagsgesellschaji mbH. 0-6940 Weinheim. 1988
0570-0833/88/0606-085/ $ 02.50/0
85 1
EtO
k.3
,OEt
R'
R2
1
1
0
0
O
The direct use of doubly metalated 1,3-dicarbonyl compounds 2 . 2 M e could make the circuitous route via tetradonor-substituted allenes 1 or silyl enol ethers 3 superfluous. The malonic ester dianion serves as model species
thereby, since it can be regarded as a tetradonor-substituted allene 1 (R' = R2 = O', OM).[91
Metalation of malonic ester 4 in the presence of two
equivalents of methylmagnesium iodide 5 in tetrahydrofuran (THF) at -78°C followed by addition of a half equivalent of oxalyl chloride 6 and subsequent work-up with
aqueous ammonium chloride solution furnished tetraammonium hexakis[tetraethyl-2,3-dioxobutane-1,1,4,4-tetracarboxylato(2 -)-O",O' : 03,04']tetramagnesate(4-) 7 as
colorless crystals in ca. 40% yield. If, however, 4, 5 , and 6
are allowed to react in the molecular ratio 1 : 1 :0.25, the
yield of 7 is increased to 85%. Careful hydrolysis of 7
1. MeMgI
reacts with bromotrimethylsilane/pyridine to give tetraethyl 2,3-bis(trimethylsilyloxy)- 1Jbutadiene- I , I ,4,4-tetracarboxylate 9.
When the ratio of the reactants 4 :5 : 6 = 1 : 1 :0.25, 7 is
formed in a two-step mechanism via the malonic ester
monoanion. Evidence against formation of the "dianion
1" ( R ' = R2 = OMgI) as intermediate is provided by the
finding that only one volume equivalent of methane is
formed upon reaction of 4 and 5 in the molar ratio 1 :2 at
-78°C. Liberation of the second volume equivalent of
methane (based on the yield of 7) is first observed upon
dropwise addition of 6. This is consistent with participation of the system monoanion/rnethyl-Grignard reagent in
the formation of 7 .
The 'H- and I3C-NMR spectra of 7 are impressively
simple [empirical formula of 7 : CQ6HIZ0060Mg4(NH4)4:
T,
symmetry, eight (!) I3C-NMR signals] and thus provide no
detailed information whatsoever about its structure. We
therefore carried out an X-ray structure analysis of 7 : this
revealed that 7 is present in the crystal in the form of a
tetraammonium salt of the first known adamantoid tetramagnesium chelate complex. [Graphical representation of
.,
Fig. I . Graphicill representdrion (whematic) o f 7
Y
5
0
2.
c,-
6
0
EtO uOEt
3. NH4CI/H20
4
Me3Si
H\
EtOm
CO E t
E
O
I
I
0
Et02C
6
\
t
,
I
0
EtO,C
'u
8
0
\ G k L
9
(pH = 5 , 20°C, 2 minutes' ultrasonication) affords tetraethyl 2,3-dihydroxy-l,3-butadiene-l,l,4,4-tetracarboxylate
8 (keto-enol equilibrium). Compounds of type 8 were
hitherto unknown. So far 8 could not be obtained in analytically pure form since it readily undergoes an acid cleavage to give two equivalents of malonic ester and one
equivalent of oxalic acid. It can be reconverted into 7 by
reaction with sodium hydride, magnesium bromide and
aqueous ammonium chloride solution. If zinc bromide is
used instead of magnesium bromide it is possible to prepare the zinc complex analogue of 7 from 8. Compound 8
852
Q YCH Verlagsgesell.~chufrmbH. D-6940 Weinheirn, 1988
Fig. 2. Stereographic projection oS the chelate complex anion of 7 with
crystallographic labeling of the skeletal atoms. Large and small black dots
indicate Mg and 0 atoms respectively, circles C atoms. Unlabeled C and 0
symbols stand for C 0 2 E t and OEt respectively. The atomic positions of the
terminal groups are very inaccurate and were only isotropically refined. The
compound crystallizes with one equivalent of 2,3-dihydroxy-2,3-dimethylbutane 1141 in the triclinic system, PT, a = 1875.6(12),b=2007.2(7),c = 1777.1(9)
pm,a=103.93(3),~=93.50(5),y=90.45(4)",Z=2,p,,,,,,=1.169gcm-',8508
hkl with F > 3 u ( F ) , R=0.144. Further details of the crystal structure investigation are available on request from the Fachinformationszentrum Energie,
Physik, Mathematik GmbH, D-7514Eggenstein-Leopoldshafen2 (FRG), o n
quoting the depository number CSD-52856,the names of the authors, and
the journal citation.
0570-0833/88/0606-0852 $ 02.50/0
Angew. Chem. inr. Ed. Engl. 27 (1988) No. 6
the chelate complex (schematic) in Fig. 1 ; stereographic
projection of the chelate complex in Fig. 2]."(" The core
of the chelate complex anion of 7 forms a tetrahedron of
four magnesium ions; these are coupled via each of the
six edges of the tetrahedron by a tetradentate tetraethyl2,3-dioxobutane- 1, I ,4,4-tetracarboxylato(2 - ) bracket such
that each of the four magnesium ions is octahedrally surrounded by six oxygen atoms.
The spectroscopic data of the zinc chelate complex differ only slightly from those measured for the corresponding magnesium chelate complex 7.
191 Cf. also P. Knochel, J. F. Normant, Tetrahedron Lett. 27 (1986) 1043
[lo]
For the topology of the chelate complex anion of 7 and its potential
applications, cf. the spherical tricycles 1 [ I I , 121 and 11 112. 131.
y
I
CH3
Experimental
7 : A suspension of 5 (60 mmol) in anhydrous T H F (150mL) was treated
(under NI. -78°C) within 30 min with a solution of 4 (9.6g, 60mmol) in
T H F (50 mL) and the resulting mixture stirred for 2 h at -78°C. It was then
treated dropwise within 1 h with a solution of oxalyl chloride (1.9 g,
15 mmol) i n T H F (50 mL), heated to 20°C within 18 h, and worked-up with
aqueous ammonium chloride solution. Yield: 5.1 g (85%), decomp. 180°C
(from acetone).-IR (KBr): i.= 1690 (C=O), 1635 c m - ' (C=C).-'H-NMR
(400 MHz. CD,OD): 6 = 1.19 and 1.28 (each t, 72 H ; 24 CH?), 3.95,4.06,4.17,
and 4.27 (each mc, 4 8 H ; 24 CH2), 4.84 (s, 16H: 4 NHT).-"C-NMR (100.5
MHz. CI1,OD): 6 = 14.56 and 14.60 (24 CH,), 61.22 and 61.71 (24 OCH2),
96.10 (I?= C ) , 169.57, 172.01, and 186.31 (24 C - 0 , 12 C=O).
9 : A suspension of 7 (1.2g. 0.5 mmol) in water (100 mL) was treated with a
solution of aluminum sulfate (15 g) in water (50mL) and the mixture ultrasonicdted for 2 min. The aqueous phase was extracted twice with 100 mL of
dichloromethane and the combined extracts dried over sodium sulfate. After
removal of solvent the remaining enol 8 (reddish oil) was dissolved in 20 mL
of diethyl ether (under N,) and treated with 0.5 g (6 mmol) of pyridine and
4.6 g (30 mmol) of bromotrimethylsilane. The mixture was then stirred for I h
at 20°C and filtered. After removal of solvent, the remaining silyl enol ether
9 (orangc colored oil) was freed of all volatile impurities at 20°C under vacuum. Yield. 1.5 g (95%). Decomp.=55'C.-IR
(film): G = 1725 (C=O), 1630
c m ' (C=C).-'H-NMR (400 MHz, CDCII): 6=0.20 (s, 18H: 2 Si(CH,),),
1.17 (t, 6 H : 2 CH,), 1-23 (t, 6 H ; 2 CH3),4.09 ( q , 4 H ; 2 OCH2),4.18(q, 4 H : 2
OCH2) -"C-NMR (100.5 MHz, CDC13): 6=0.35 (2 Si(CH,),), 13.75 (2
CH,), 14.01 ( 2 CH,), 60.79 (2 OCH,), 60.97 (2 OCHz), 113.25 (2 =C), 156.46,
163.59, and 164.1 I (0-C=O and =C-O).-MS
(70 eV): m / z 518 ( M a ) .
Received: February I, 1988;
supplemented: March 9, 1988 [ Z 2600 IE]
German version: Angew. Chem. I00 (1988) 878
CAS Registry numbers:
4, 105-53-3: 5, 917-64-6; 6, 79-37-8; 7, 114446-10-5; 7 analogous zinc complex, 114466-56-7; 7 .2,3-dihydroxy-2,3-dimethylbutane,114446-11-6: 8,
114446-12-7: 9, 114446-13-8; MeISiBr, 2857-97-8.
[I] Reviews. A. Maercker, M. Theis, Top. Curr. Chem 138 (1987) I ; P. von
R. Schleyer, Pure Appl. Chem. S6 (1984) 151.
[2] J. Vollhardt, H.-J. Gais, K. L. Lukas, Angew. Chem. 97 (1985) 607; Angew. Chem. Int. Ed. Engl. 24 (1985) 610.
[3] J. Vollhardt, H.-J. Gais, K. L. Lukas, Angew. Chem. 97 (1985) 695; Ang e s . Chem. Int. Ed. Engl. 24 (1985) 696; for further I,l-dilithioalkyl
phenyl sulfones cf.: J. J. Eisch, S . K. Dua, M. Behrooz, J. Org. Chem. 50
(1985) 3674: M. C. Mussatto, D. Savoia, C. Trombini, A. Umani-Ronchi. ihrd. 45 (1980) 4002; A. Roggero, T. Salvatori, A. Proni, A. Mazzei,
J Orgunornet. Chem. 177 (1979) 313; K. Kondo, D. Tunernoto, Tetrahedron Lett. 16 (1975) 1397: J. B. Evans, G. Marr, J . Chem. SOC. Perkrn
Truns. I 1972, 2502: E M. Kaiser, L. E. Solter, R. A. Schwarz, R. D.
Beard, C. R. Hauser, J . Am. Chem. SOC. 93 (1971) 4237; cf. also 1,odilrthiobis(trimethyIsilyl)methyl phenyl sulfone: W. Hollstein, K.
Harms, M. Marsch, G. Boche, Angew. Chem. 99 (1987) 1279; Angew.
Chem. In!. Ed. Engl. 26 (1987) 1287.
[4] S. P. J. M. van Nispen, C. Mensink, A. M. van Leusen, Tetrahedron Lett.
2 / (1980) 3723.
[ 5 ] W. Carruthers: Some Modern Methods of Organic Synthesis. 2nd edit.,
University Press, Cambridge 1978, p. 1 ff.
[6] E. J. Corey, Pure Appl. Chem. 14 (1967) 19; D. Seebach, Angew. Chem.
91 (1979) 259: Angew. Chem. I n t . Ed Engl. 18 (1979) 239; T. A. Hase:
Umpofed Svnthons, A Survey of Sources and Uses in Synthesis. Wiley,
New York 1987.
[7] R. W. Saalfrank, W. Rost, Angew. Chem. 97 (1985) 870: Angew. Chem.
In!. Ed. Engl. 24 (1985) 855; R. W. Saalfrank, F. Schutz, U. Moenius,
Swu/ie.si.%1985, 1062; R. W. Saalfrank, K. Hilbig, F. Schutz, K. Peters, H.
G. von Schnering, Chem. Ber. 121 (1988), in press.
181 R. W. Saalfrank, M. Hanek, Tetrahedron 44 (1988), in press.
Angew ('hem.
In1
3
Ed. Engl. 27 11988) No. 6
I: x
=
II: R
(CHZ),; 0
=
(CHz),
[ I I] J. M. Lehn, Angew Chem. 100 (1988) 9 1 ; Angew. Chem. Int. Ed. Engl. 27
(1988) 89: Pure Appl. Chem. 49 (1977) 857; E. Graf, J. M. Lehn. J . Am.
Chem. SOC.97 (1975) 5022.
[I21 E. Weber, F. Vogtle, Kontakte 1981. No. I , p. 24; E. Weber: Phase
Transfer Catolvsts. Properries and Applications (Merck-Schuchardt 1987).
p. 33.
[ 131 F. P. Schmidtchen, Angew. Chem. 89 (1977) 75 I ; Angew. Chem. lnt. Ed
Engl. 16 (1977) 720: Nuchr. Chem. Tech Lab 36 (1988) 8.
[I41 2,3-Dihydroxy-2,3-dimethylbutaneis formed as by-product in the synthesis of 7 from oxalyl chloride 6 and methyl-Grignard reagent 5 .
Preparative UV-Laser Photochemistry:
A Biscarbene Intermediate in the Synthesis of a
5,6-Dihydrodibenzola,elcycloocteneContaining a
trans-Double Bond * *
By Klaus Hannemann* and Jakob Wirz
The extremely high light intensities of laser light sources
enable multiphoton processes to be achieved which cannot
be initiated with conventional lamps. These multiphoton
processes were hitherto primarily investigated spectroscopically ;"I in some cases new products have been isolated."]
Depending upon the time interval between the absorption
processes, multiphoton processes range from quasi-simultaneous multiphoton absorption to secondary excitation of
singlet and triplet
to photochemical reactions of
reactive intermediates.[2g-J1
A further interesting case is the
photolysis of dichrom~phores.[~]
If both chromophores of
a dichromophoric molecule are excited with high-intensity
light, a difunctionally reactive intermediate can be formed
which may lead to new products. As an example of a dichromophoric system we chose the bis(diaz0methane) 1,
and describe here the preparative laser photolysis of 1 as
compared to its conventional photolysis.
The bis(diazo) compound 1IS1 was prepared from the
bishydrazone of o,o'-dibenzoyl(bibenzyl)LZ'l by oxidation
with activated manganese(1v) oxide. As shown in Scheme 1
conventional irradiation of the starting compound 1 leads
to the hydrocarbons 7-9I6l and to small yields of the novel
cyclic azine 10, which is formed via an intramolecular
carbene addition to the remaining diazo group of 2. The
formation of the hydrocarbons 7 - 9 can be readily
[*I
['I
["*I
Dr. K. Hannemann ['I, Prof. Dr. J. Wirz
Institut fur Physikalische Chemie der Universitat
Klingelbergstrasse 80, CH-4056 Basel (Switzerland)
New address: Ciba-Geigy AG-K410.4.02Postfach, CH-4002 Basel (Switzerland)
This work was supported by the Fonds der Chemischen Industrie (Liebig Stipendium fur K . If.), by the Schweizerischer Nationalfonds zur
Forderung der wissenschaftlichen Forschung (Project No. 2.034-086)
a n d by the Ciba Stiftung.
0 VCH Verlagsgesellschafr mhH. 0-6940 Weinherm. 1988
0570-0833/88/0606-0853 $ 02.50/0
8 53
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