close

Вход

Забыли?

вход по аккаунту

?

Nucleophilic Elimination-Cycloaddition of -Alkanediyl Bis(triflates) a Novel Method for the Synthesis of Metallacycles with Reactive Metal-Carbon Bonds.

код для вставкиСкачать
141 For interesting aspects of the chemistry of electron-deficient trinuclear clusters of the early transition elements see: A. Bino, F. A. Cotton, Z. Dori, Inorg.
Chem. Acta 33, L133 (1979); A. Miiller, R. Jostes, F. A. Cotton, unpublished
results.
[S] (41 forms monoclinic crystals with a = 15.661(3), b = 18.807(3), c=6.552(1)
p = 116.39(2)", space group Cm, Z = 2 , p,,,,=2.14 g.cm-'; 1985 independent reflections (Synlex P2, diffractometer. 2%,,, = 54.0". Mo~,.);R=3.1%.
[6] Cf. H Vahrenkamp. Angew. Chem. 87,363 (1975); Angew. Chem. Int. Ed.
Engl. 14, 322 (1975).
171 T. E. WovJ 3. M. Berg, C. Wurrrck, K. 0.Hodgson, R. H. Holm, R. B. Frank d , J . Am. Chem. SOC. 100, 4630 (1978); G. Chrisfou. C. D. Garner, F. E.
Mabbs. T J. King, J. Chem. SOC.Chem. Commun. 1978. 740.
[S] A Mufler. W Jaegermunn, Inorg. Chem. 18, 2631 (1979).
191 A. Miiller. P. Christophliemk, Angew. Chem. 81, 752 (1969); Angew. Chem.
Int. Ed. Engl. 8,753 (1969); cf. also M. G. B. Drew, P. C. H. Mitchell, C. E
Pygall, rbid. 88, 855 (1976) and IS, 784 (1976). respectively.
A,
Table 1. IR and MS data and melting points of the heterocycles ( I ) and (2)
v(C0)
[cm-']
2060 m [a]
1993s
1976 vs
1946 s
2062 m [a]
1996s
1978 vs
1944s
2059 m [a]
1995 s
1973 vs
1943s
m/e(M+)
410
438
424
M.p.["C]
118
108
94
2098 m [b]
2046 s
2022 vs
1984s
2072 m [c]
2008s
1985 vs
1960s
1170s[d]
1035 s
1611 m[c]
502 [el
452
102 (dec.)
[a] In n-hexane. [b] In CHCI,/CCIa ( 1 :l). [c] In CCI,. [d] In KBr. [el Field desorption.
Nucleophilic Elimination-Cycloaddition of a,oAlkanediyl Bis(triflates), a Novel Method for the
Synthesis of Metallacycles with Reactive MetalCarbon u Bonds[']
By Ekkehard Lindner and Hans-Jurgen Eberle'']
Dedicated to Professor Gerhard Fritz on the occasion of his
60th birthday
Heterocycles with metal-carbon u bonds have recently
been the subject of numerous detailed investigations, since
they play an important role as intermediates in transition
metal catalyzed reactions[21and in organic
In the
search for new general methods for the synthesis of such
compounds having aliphatic ring systems of various sizes we
have examined the reaction of dianionic manganese comp l e x e ~ l[(OC),Mn(PR,O)]'~~
with alkane derivatives containing the carbenium ion-stabilizing trifluoromethanesulfonate moiety ("triflate") in the a,w-position as favorable
leaving group.
Ph
Ph
X.
Fig. 1. ORTEP diagram of ( l a ) (vibrational ellipsoids correspond to 50% probability density).
["I
Bond lengths [pm]
Angles
Mn3 C4
C4 CS
C5 C6
C6 0 1
0 1 P2
P2 Mn3
P2 Mn3 C4
Mn3 C4 C5
C4 C5 C6
CS C6 0 1
C6 0 1 P2
0 1 P2 Mn3
221.0(3)
151.8(7)
148.0(7)
144.4(4)
161.1(2)
227.1(1)
92.1(1)
118.7(2)
117.2(4)
112.8(3)
1202(2)
116.4(1)
( l a ) , X = CH2
Z = OS02CF3
At 20 "C the variously nucleophilic centers of
[(OC),Mn(PPh20)]2- attack the terminals of the hydrocarbon chain almost simultaneously with elimination of
CF3S07 . This pseudosynchronous mechanism hinders P-hydrogen elimination. Owing to the chelate effect, the colorless
metallacycles (1) are thermally stable; they sublime in a high
vacuum and are soluble in all the common organic solvents.
They were characterized by complete elemental analysis, IR,
mass spectra (Table I), and 'H-NMR spectra [e.g. (la), C6D6
rel. to TMS: 6 = 1.04 (td; J = 6.4 Hz, Mn--CH2--CH2; J = 2.1
Hz, P - Mn -CH2), 1.92 (m; CH2--CH2---CH2), 3.79 (dt;
J = 15.3 Hz, P---O---CH,; J=4.7 Hz, O--CH2- -CHI)]; ( l a )
was additionally characterized by an X-ray crystal structure
analysi~'~].
The six-membered ring of (la) has a distorted chair shape
with dihedral angles of 130.6 and 164.2'. The Mn3 --C4 distance is markedly greater than the sum of the single bond
radii. Substantial widening of the tetrahedral angle is indicative of a highly strained ring. The deviation of C6 from the
plane formed by C4, C5, 01, P2 effects slight distortion of
['I
0181
the tetrahedral angle. The trans CO-ligands are bent inwards
to the heterocycle (ClO-- Mn3---C8 164.9(2)").
The MnC u bond is extremely reactive. Thus the action of
liquid SO2 or CO on (16) and ( l c ) leads via an insertion reaction to the expanded, colorless heterocycles (2b) and (2c)
which are soluble only in polar solvents (cf. Table 1).
We have thus demonstrated the first instance of CO insertion in the M--C bond of a metallacycloalkane.
Ph
Experimental
Prof. Dr. E. Lindner, Dipl.-Chem. H.-J. Eberle
Institut fur Anorganische Chemie der Universitat
Auf der Morgenstelle 18, D-7400 Tiibingen 1 (Germany)
Angew. Chem. Int. Ed. Engl. 19 (1980) No. 1
The heterocycle (1) is obtained by dropwise addition of a
solution of Na2[(OC)4Mn(PPh,0)] (1 mmol) in dimethyl
0 Verlag Chemie. GmbH, 6940 Weinheim. 1980
0570-0833/80/0101-0073
$
. 02..50/0/0
73
ether (DME) (50 ml) to a solution of ZCH, -X CH2Z (1
mmol) in DME (30 ml) at 20 "C. After 1 h the solvent is removed in a high vacuum and the residue is extracted with nheptane at 40°C. After filtration (D3), the n-heptane is removed and (1) is sublimed at ca. 100°C in a high vacuum.
Yield 15--56%.
(Ib) (0.5 mmol) is allowed to react in 30 ml of liquid SOz
for 1 h at - 60 "C. After removal of SOz, (2b) is obtained in
quantitative yield.
A solution of ( l c ) (0.5 mmol) in n-heptane (15 ml) is transferred to an autoclave and subjected to a CO pressure of 300
bar at 80°C. After 16 h, analytically pure (Zc) crystallizes
from the solution in 80% yield.
~
In neither case does the fluorite structure occur with the
ideal composition ZrO, and "Li2No.sClo.,-".
These structural properties prompted us to characterize
lithium nitride chloride with respect to ionic conductivityl21
and thermodynamic properties. The studies were extended to
other lithium nitride halides for purposes of comparison. We
found all the compounds listed in Table 1 to have a high lithium ion conductivity and negligible electronic conduction.
Table I . Activation energy EA (products of ionic conductivity and absolute temperature), decomposition potentials U,,,, and free energy of formation AO; of
the lithium nitride halides from the elements in their standard states [a].
Lihh7N,u,l and Li, 17N2701are different stoichiometries of the same phase.
L T = low temperature modification, H T = high temperature modification.
Received: July 24, 1979 [Z 374 IE]
German version: Angew. Chem. 92, 70 (1980)
[I] Preparation and Properties of, and Reactions with, Metal-Containing Heterocycles, Part 4. This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen 1ndustrie.-Part 3: E. Lindner, G
Funk, S. Hoehne. Angew. Chem. 91. 569 (1979). Angew. Chem. Int. Ed. Engl.
18, 535 (1979).
121 D. E. Webster. Adv. Organomet Chem. 15, 147 (1977); R. H. Grubbs. A.
Miyushifu, J. Am. Chem. SOC.100. 7416 (1978); U. Schubert. A. Rengstl. J.
Organomet. Chem. 166. 323 (1979).
[3] M. I . Bruce, Angew. Chem. 89.75 (1977); Angew. Chem. Int. Ed. Engl. 16,73
(1977).
141 E. Lindner, G. uun Au,
Eberle, 2. Naturforsch. B 33. 1296 (1978).
IS] (lo) forms monoclinic crystals from n-hexane (space group P2,/c). u = 913(2),
b = 1371(2),~=1646.4(3)pm,P=l15.39(2)".
2 = 4 , pL.,,,=1.462g.cm ' The
structure was solved by Patterson and difference Fourier syntheses and anisotropically refined to R=0.036 (apart from H) for 2318 independent reflections with program system SHEL-76.
Lif x N o ~ C ~ O ,
Lil,N,Cl2
Li,NBr,
LillN4Br(LT)
Li,,N,Br (HT)
LisN12 (LT)
LisN12 (HT)
Llhh7N~WI
LiY 2 2 %
u,,,
EA
lev1
IVl
0.49
0.83
0.46
0.73
0.47
0.50
0.44
0.55
0.80
2.52
1.86
21.30
1.32
0.66
1.96
I .63
0.92
0.92
Ab:
[kJ/gAtom]
T
["C]
- 185
- 154
101
332
176
146
300
98
287
313
316
- 138
- 124
- 90
[a] The energies of formation of the binary lithium halides were taken from
standard tabulations 151.
The logarithms of the product of the conductivities (obtained by AC measurements) and the absolute temperature
are plotted as a function of the reciprocal temperature in Figure 1. The relation obeys an Arrhenius law for the diffusion
constant of the ions.
-
Lithium Nitride Halides-New Solid Electrolytes
with High Li' Ion Conductivity
T
[TI
By Peter Hartwig, Werner Weppner, Winfried Wichelhaus,
and Albrecht Rubenad']
Dedicated to Professor Harry Hahn on the occasion of his 65th
birthday
Hahn et al.lil have examined the existence of ternary lithium-nitrogen-halogen compounds on the quasibinary
Li,N-LiX cut (X = C1, Br, I) of the Gibbs phase triangle LiN-X. For LigNzCl3,the LiC1-richer phase of the two lithium
nitride chlorides, an antifluorite structure was found in
which 10% of the lithium sites are vacant while the anionic
partial lattice is almost completely occupied by N and C1. In
order to underscore the cationic underoccupation of the antifluorite phase, we choose the designation Li18N,, 4C10.6.
On interchanging the anionic and the cationic lattices, an
analogy is seen to exist with a series of known solid oxygen
and fluorine ion conductors, e. g. Zr02 doped with 20 mol-%
of CaO.
15
20
25
30
T'' 1031~-11-.
Fig. I. Temperature dependence of the product ofelectrical conductivity and absolute temperature of the lithium nitride halides.
Coordination
Cubic
Z ~ O
No X 1 o 6
Tetrahedral
2
0 1 8 00,
Li, S
~
O
,
Fluorite type
02-ion conductor
Antifluorite type
Li ion conductor
+
[*] Prof. Dr. A. Rabenau. DipLChem P. Hartwig. Dr. W. Weppner. Dr. W. WI-
chelhaus I"]
Max-Planck-Institut fur Festkorperforschung
Heisenbergstrasse 1. D-7000 Stuttgart 80 (Germany)
[**I Present address: Jenaer Glaswerk Schott & Gen., D-6500 Mainz, Germany.
74
0 Verlug Chemie, GmbH, 6940 Wernheim, 1980
It is seen that the conductivity of the antifluorite phase
Li, *NO.,Cl0 6 is greatest over the entire temperature range; at
the same time, the activation energy of 0.49 eV is comparatively low. The discontinuities in the conductivities of
Lil3N4BrI31and Li,NI, are attributed to kinetically strongly
inhibited phase transitions which are confirmed by calorimetric measurements. The Li,N-richer phase of the two lithium nitride iodides is the only compound to exhibit a relatively wide phase width, extending at least from Li6,,Nt ,,I
to Lip,,N2 761(Li3N :LiI = 1.89 to 2.76). The ionic conductivity increases by several orders of magnitude with increasing
0 5 7 0 - 0 8 ~ ~ / ~ 0 / 0 1 0 1 - 0 0 7$02.50/0
4
Angew. Chem. I n t . Ed. Engl. 19 (1980) No. I
Документ
Категория
Без категории
Просмотров
0
Размер файла
222 Кб
Теги
bond, cycloadditions, method, triflate, reactive, elimination, metallacyclus, synthesis, metali, alkanediyl, bis, novem, carbon, nucleophilic
1/--страниц
Пожаловаться на содержимое документа