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Mixed Oligomers of Propellanes and Bridged Annulenes with Bis(maleimides) and Bis(triazolinediones) Studied by 252Cf-Plasma Desorption Mass Spectrometry.

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Mixed Oligomers of Propellanes and Bridged
Annulenes with Bis(ma1eimides) and
Bis(triazo1inediones) Studied by 252Cf-Plasma
Desorption Mass Spectrometry[*']
By P. Ashkenazi, R. D. Macfarlane, W. A. OertIing,
In view of the results described in the preceding paper131
and in view of the existence of bi~(maleimides)[~1
we decided
to study mixed oligomers of tetraenic propellanes and
bridged annulenes with both the bis(triazo1inedione) type of
dienophile (12)13.51
and with the bis(ma1eimide) type (8).
Heinrich Warnhofl, K. M . Wald, and David Ginsburg"'
Dedicated to Professor Rorf Huisgen on the occasion of
his 60th birthday
On using propellanes as stereochemical models in various
types of reactions, we discovered that for steric reasons simple substituted maleimides attack tetraenic propellanes from
the side anti- to the heteroring'". In contradistinction to
maleimides, substituted triazolinediones contain nitrogen
atoms whose antisymmetric n- combination of lone pair orbitals (HOMO) can undergo secondary orbital interactions
with the CO T* orbitals (LUMO) of the propellane hetero
ring causing syn-attack with reference to the carbonyl-containing rings"].
Before we began our work we knew that a tetraenic propellane mono-Diels-Alder adduct with a substituted maleimide, e.g. (2), will react with a simple triazolinedione such
as (3) to give (4) and with another mole of a maleimide also
to give the same type of anti-syn-bisadduct (4). On the other
hand, the monoadduct (6)with the substituted maleimide (7)
does not afford a bisadduct even under forcing conditionsl6I.
191
18al Y = -(CH,)s.
I8bl Y = -@CH2-@
18cI Y =
@
Table 1. Reaction of dlenes ( 1 ) and (9) with (8) in a molar ratlo of 2: 1
~
Diene
11)
(1)
Dienophile
ProdUCt
M. p.
I"C1
@a)
18b)
1 W
I 1Ob)
200
( I OC)
11 1 )
216
232
(1)
191
195
M. wt
calc.
exp.
703
785
695
643
704
786
696
644
Table 1 lists 2: 1 compounds (10) prepared from tetraenic
propellane ( I ) and three different bismaleimides (8a-c) as
well as the 2 : 1 adduct ( 1 1 ) of 1.6-methano[lO]annulene (9)
Me n
(6)
(5)
We assume in our subsequent argument, albeit without ironclad proof, that the bisdienophiles behave analogously to the
monofunctional dienophiles.
['I
with (Sb). When (1Oa) and (lob) (Table 1) were treated with
(12), the compounds (13a) and (13b), respectively, were obtained (Table 2). Compound (13a) was accompanied by the
Dr. P. Ashkenazi, Prof. Dr. D. Ginsburg ['I
Department of Chemistry, Israel Institute of Technology
Haifa (Israel)
Prof. Dr. R. D. Macfarlane. Dr. W. A. Oertling
Department of Chemistry. Texas A & M University
College Station. Texas 77843 (USA)
Prof. Dr. H. Wamhoff, Dr. K. M. Wald
Institut fur Org. Chemie und Biochemie der Universitat
Gerbard-Domagk-Strasse 1, D-5300 Bonn (Germany)
+
110a-cl Y as in I81
] T o whom correspondence should be addressed.
['*I
Propellanes, Part 61. We are grateful to the National Science Foundation
and the Robert A Welch Foundation for support of the mass spectral work /R.
D. M. and W. A. 0.)
without which publication of these results would not have
been possible. Support by the Deutsche Forschungsgemeinschaft and by Bayer
AG is gratefully acknowledged (H.W. and K . M. W.).We thank Prof. Dr. A
Mandelbaum for drawing our attention to "*Cf plasma desorption mass spectrometry, and Prof. Dr. E. Vogei for samples of bridged annulenes and for his interest in this work.-Part 60: [3].
936
0 Veriag Chemie, GmbH, 6940 Weinheim, 1980
Table 2. Reaction of dienes (10) with dienophile (12) in a molar ratio of 1 : 1
Diene
OS70-0833/80/1111-0936
Dienophile
$02.50/0
Product
M. wt.
M.p.
I"Cl
calc.
exp.
Angew. Chem. Int. Ed. Engi. 19 (1980) No. I 1
Me 0
N-4
/
[13a,bl
Y as
in (81
1: 1 adduct of (1Oa) with (12) [M.wt. 983 (calc.); 984
(found)], whilst (13b) showed no such analogue in the mass
spectrum, but was rather accompanied by the product containing eight equiv. of ( I ) , 4 equiv. of (Sb), and 4 equiv. of
(12) [M.wt. 4260 (calc.); 4269 (found)]. The molecular
weights were determined by 252Cfplasma desorption mass
spectrometry (cf. [,I); all other analytical methods of structural elucidation failed.
p-CH2[(q5-C5H5)Rh(CO)]2~t]
and the smooth spontaneous
formation of (q5-C5H5),Rh3(p-CO), from the p-hydrido
complex [(y5-C5Hs)zRh2(C0)3H]BF4have demonstrated the
activation of basic molecular centers to constitute a powerful
alternative method of metal-metal bond makingi2].We now
report the synthesis of a simple dinuclear rhodium compound which is accessible from its mononuclear precursor
neither by thermal nor by light-induced reactions.
The action of tetraffuoroboric acid on diethyl ether solutions of dicarbonyl(qs-pentamethylcyclopentadieny1)rhodium (1) effects fast and complete precipitation of an ionic, exceptionally base-sensitive dark brown complex (2), which is
thermally stable up to about 85 "C and is shown by its properties (Table 1) to be a cationic p-hydrido complex (Scheme
1). The intermediacy of the primary protonation product
[(q5-C5Me5)Rh(C0)2H]BF4in the formation of (2) is evidenced by independent protonation experiments carried out
in n-pentane['] and similar reactions of the cobalt complex
(q5-C5H,)Co(PMe,)2, related to (1) for which Werner et al.
have observed a variety of surprising secondary reactions of the
mononuclear hydrido complex [(q5-C5H,)Co(PMe3)2H]BF4[31.
The most striking property of the nitromethane-soluble
compound (2) is its proclivity to undergo deprotonation,
which is slow with basic solvents (dimethylformamide, dimethy1 sulfoxide, acetonitrile) but fast and quantitative with sodium methoxide/methanol (Scheme l); the violet-red neutral complex (3) is isolated which, strangely enough, was
hitherto unknown (Table 1).
I71
Received: June 2, 1980 [Z 612b IE]
German version: Angew. Chem. 92, 972 (1980)
1
CAS Registry numbers:
( I ) , 16609-30-6; (Ba),4856-87-5; (Sb), 13676-54-5; (Xc), 3278-31-7; (9). 2443-46-1;
(foal, 75495-29-3; (lob). 15495-30-6 (lor), 75495-31-7; ( I I ) , 75506-22-8; (12).
38727-98-9 (13a), 75506-23-9; (1361, 75495-32-8
111 M. Kafrory, M. Peled, D.Ginsburg. Helv. Chim. Acta 62, 1326 (1979).
[2] R. Gleiter, D. Ginsburg, Pure Appl. Chem. 51, 1301 (1979), and reference
cited therein.
131 P.Ashkenazi, R. D. Macfarlane, W. A. Oertling. H. Wamhoff, K. M. Wald. D.
Ginsburg. Angew. Chem. 92.970 (1980): Angew. Chem. Int. Ed. Engl. 19,933
(1980)
141 R J. Cotter, C. K. Sauers, J. M . Whelan, J. Org. Chem. 26, 10 (1961); P.
Kouac~c,R. W. Hein, 1. Am. Chem. SOC.81, 1187 (1959)
[ 5 ] K. Wafd, H. Wamhofl Chem. Ber. 111, 3519 (1978); K B. Wagener, S. R.
Turner. G. B. Butler, J. Polym. Sci. Polym. Lett. 10, 805 (1972).
[6] M . Peled. D.Ginsburg. unpublished results.
A Simple Method of Forming Metal-to-Metal
Bonds["]
By Johann Plank, Doris Riedel, and
Wolfgang A. Herrmann[']
Our studies on the acid-induced formation of trinuclear
methylidynerhodium clusters from the methylene complex
I*]Prof. Dr. W.
A. Herrmann, Dr. J. Plank, D. Riedel
Instirut fur Chemie der Universitat
Universitatsstrasse 31, D-8400 Regensburg 1 (Germany)
[**I Syntheses of Metal Carbonyls, Part 6. This work was supported by the
Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie, Degussa Hanau and Hoechst AG.-Part 5: W. A. Herrmann, H. Biersack, J. Organometal. Chem. 191, 397 (1980).
Angew. Chem Inr. Ed. Engl. 19 (1980) No. I t
Scheme I
Table 1. Physical and spectroscopic properties of the new rhodium complexes (2)
and (3).
(2): dark brown powder, can be stored indefinitely with rigorous exclusion of
light and moisture, decomposes above ca. 85°C (m.p. >24O"C, sealed capillary). Readily soluble and stable in nitromethane. Equtvalent conductivity
mol/l): A=137 cm2 mol ~' 0 - ' . IR (0120;
(CH,N02, 21.6"C, c = 3 . 0 x
cm-'): 2010 vs, 1836 s (KBr) [a]; 2022 vs, 1834 vs (CHINO2); 2026 vs, 1839 vs
(CHK12). 'H-NMR (90 MHz; CDIN02, -25°C): 6=2.03 (s. 30H), - 10.40 (t,
1H: 'J~h.H=19.2Hz)
(3): carmine red powder or violet-red. light-sensitive needles; stable in air for several days at room temperature in the dark. Sinters at 141-143 "C (sealed capillar y ) with weak evolution of gas and formation of the deep blue derivatlve (4).
Readily soluble in THF, CH,C12, and benzene; equivalent conductivity (THF,
mol/l): A = 1 . 1 cm2 m o l - ' 0.' (non-electrolyte) IR
21.6"C. c = 2 . 8 x
( K O cm-I): 1947 vs, 1794 vs (KBr); 1952 vs. 1791 vs (THF); 1951 vs, 1778 vs
(CHzCI,). 'H-NMR (90 MHz; [D&THF. - lO'C): 6= 1.91 ("s"); MS (12 eV);
TQ 140"C, TE 110°C): m / e = 5 6 0 ( M i , 11%); 532 ( [ M - C O J t , 100). 504
( [ M - 2 C O j t . 4). 476 ([M-3CO] ?, l ) , 373 ((CsMeS),Rh?. 82)
[a] IR spectra of KBr disks prepared in air already show the C O bands of product
(3) alongside the wC0 absorptions of (2).
0 Verlag Chemie, GmbH, 6940 Weinhelm. 1980
0570-0833/80/1I11-0937
$02.50j0
937
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252cf, propellanes, bridge, mixed, spectrometry, maleimido, mass, triazolinediones, annulene, oligomer, bis, plasma, studies, desorption
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