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Crown Arsanes; Air-Stable Multielectron Ligands for Transition Metals.

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Ph
l5a) , 6 2%
they endow their transition metal complexes with chirality;
the stable iron complex (6c)14]was prepared by us and illustrates this capability. This feature could be useful in the development of asymmetric homogeneous catalysts.
(5b), 54c0
Table 1. Physical Data of the cited compounds. 'H-NMR; 6 values rel. to TMS
in CDCI,; Mass spectra 70 eV, m/e.
Compound
M.p.
orn
'H-NMR
MS
71 "C
(Ethanol)
2.2-2.9 (m; 4H.
As-CH2-CH2),
3.2 (mc; 2H.
CH2-CH=),
6.15 (mc; IH,
(m; 14H.
-CH-),
7.0-7.65
aromatic H)
372 (6%. M ' ),
(24). 227 (51).
(45). 152 (loo),
(26). 128 (48).
(34)
1.51 (s; 4H. bH2-CH2-k).
2.2-2.9 (m; 4H,
As-CH2-CH2),
5.92 ( s ; IH,
-=CH-), 7.0-7.6 (m; 14H. aromatic H)
398 (69%. M ), 229
(63). 227 (75). 169
(100). 141 (88). 129
(31). 115 (31)
2.2-3.1 (m; 4H,
As-CH2-CH2),
6.83 (s; I H ,
=-C-CH=),
7.1-7.8 (m; 20H,
Ph-CH, aromatic H)
460 (39'16, M +).432
(2). 307 (61). 231
(100). 229 (61). 227
(67). 115 (24)
1.9-2.8 (m; 4H.
As-CH2-CH2),
3.1-4.1
(m;
4H, CH2-CHPhCH), 6.3 (mc;
=CH-), 6.7-7.6 (m; 22H, aro(m: 1 H.
matic H). 8.3-8.6
N-CH)
553 (19%. M i ) , 461
(18), 324 (3). 229
(16). 227 (16). 182
(18). 93 (100)
1.6-2.8 (m; 8H.
(m;
As-CH2-CH2).
3.3-3.5
IH,
CH-).
6.15 (mc; l H ,
XH-). 6.9-7.5 (m; 24H, aromatic H)
628 (38%. M ), 399
(19). 229 (43). 227
(43), 149 (100). 128
(24). 115 (13)
10
n, =
1.6495
134°C
(Toluene)
229
219
143
115
+
The structures of the products have been determined by
mass- and NMR-spectroscopy and elemental analysis (see
Table 1).
Received: March 24. 1980 [ Z 668a IE]
German version: Angew. Chem. 93. 116 (1981)
CAS Registry numbers:
( I ) , 765-46-8; f3), 19770.38-8; (4a), 76124-28-2; (4b).76124-29-3: (4c),76124.306; (4d), 76124-31-7; (4e), 76124-32-8; (SaJ, 76124-33-9; (Sb), 76124-34-0; ( 6 ~ ) .
76124-35-1; (661, 76124-36-2. ( 6 ~ )76137-1
.
1-6; Ph2AsLi, 1906-48-4; Ph2PLi.
4541 -02-0 O--CH-Ph,
100-52-7; a-picolyl-Li, 1749-29-7: Br(CH2)2Br, 106-934;
n2"1) -
1.6259
30
nu =
1.6551
155-156°C
(Ligroin)
2.4-3.0 (m; 4H.
P-CH2-CH2),
3.25 (mc; ZH.
CH2-CH- -), 6.2 (mc; 1 H,
=- CH-). 7 0-7.9 (m; 14H, aromatic H)
200-201 "C 2.5-3.15 (m; 4H,
(Toluene)
P-CHI-CH2).
6.72 (s; 1 H,
=CH-C-.),
7.5-7.9 (m; 20H,
aromatic H)
Ph-CH-
..
21)
n, =
1.5849
20 "v -
15798
n21)_
0-
1.6434
+
344 (65%, M ), 215
+
( l o o ) , 202 (71). 201
(30). 155 (10). 115
[ I ] Th. Kauflmann, J. Ennen, H Lhotak. A. Rensing, F. Sleinseifer, A. Wolferrnann, Angew. Chem. 92, 321 (1980); Angew. Chem. Int. Ed. Engl. 19, 328
(1980).
121 in the absence of synthetic details [S. W. Sfaley. M. A. Fox, T K . Hirrel, J .
Am. Chem. SOC.98,3910 (1976)] we obtained a 58% yield by reacting a solution of indene in T H F with 2 equivalents NaNH2 and 1 equivalent 1.2-dibromoethane.
[3] Conventional count of electrons in donor ligand with transition metals.
[41 The position of the CC double bond in the five-membered ring of the indene
residue of (4d) is not clear. The compound (66) consists of a mixture of the
isomers with Cp = 1.3- or 1,4-cyclopentadienyl respectively. It should be possible to separate (6c) into two diastereomers. but to date this has been unsuccessful.
(9)
432 (54%. M +), 344
(10). 230 (100). 215
(67). 202 (57). 155
(131, 115 (8)
1.95-3.0 (m; 6H. (CH2)3), 3.3
(mc; 2H. -=CH-CH2). 6.2 (mc;
1H. .-CH-).
6.9-7.6 (m; 7H.
aromatic H), 8.35-8.6 (m; 1 H,
N-CH)
235 (21%. M + ) ,141
(7). 128 (12). 115
(10). 106 (13). 93
1.8-2.6 (m; 8H,
2.85,
2.95
(2
=CH-CH2[Cp]),
(m; 1 H, ,CH-),
(=CH-CH2[Ind]),
(m; 4H, =CH-),
7H, aromatic H),
1 H, N-CH)
CH2-CH2),
mc;
ZH,
2.85-2.95
3.3 (mc; 2H,
5.95-6.4
6.9-7.7 (m;
8.5-8.7 (m;
327 (4%. M I ), 235
(7), 185 (6). 128
(lo), 115 (5). 106
in C,D,:
2.G2.7 (m; 8H,
CH2-CH2), 2.95 (m; 2 H [Cp]),
3.7 (mc; 1 H [Cp]), 3.98 ( d 1 H
[Ind]). 4.4 (mc; 1 H [Cp]). 4.5CH-). 4.85 (d;
4.8 (m; 1 H,
(m; 7H.
1 H [Indl), 6.65-7.6
aromatic H). 8.6 (rn; 1 H,
N-CH)
381 (47%. M +), 276
(14). 142 (6). 115
(11). 106 (9). 84
(100)
(100)
(100)
Crown Arsanes; Air-Stable Multielectron Ligands
for Transition Metals[**]
By Johann Ennen and Thomas Kauffmann1'1
Dedicated to Professor Wilhelm Klemm on the occasion
of his 85th birthday
Many of the transition metal reagents and catalysts used in
organic synthesis contain ligands which do not participate
directly in the reaction ("passive ligands"[*])and which are
often not optimal (Iow stability of bonding to the metal, easily
attacked by nucleophiles, or toxic ligands such as CO or
NO). We have therefore synthesized polydentate multi, electron ligands['.*]and now wish to describe macrocyclic polyarsanes. These "crown arsanes" are air stable and are
therefore considerably easier to handle and store than the
highly air sensitive macrocyclic polypho~phanes'~].
Both
types of compounds suffer from the disadvantage however
that the isolation of pure chiral products is difficult. To our
knowledge crown arsanes were not knownI4', although open
chain polyarsanes have already frequently been used to complex with transition metal elements.
The starting materials (I), (2), (3), and (4), which are not
described in the literature, were synthesized (reactions were
r ] Prof. Dr Th. Kauffmann, Dip[.-Chem. I. Ennen
Organisch-Chemisches lnstitut der Universitat
Orleans-Ring 23. D-4400 Miinster (Germany)
The ligands with the indenyl group have the distinctive
feature, not shown by the cyclopentadienyl analogues, that
118
0 Verlag Chemie, GmbH, 6940 Weinheim, 1981
["I
Multielectron Ligands, Part 3. This work was supported by the Deutsche
Forschungsgemeinschaft. Part 2: I I ]
0570-0833/81/0101-011R
$ 02.50/0
Angew. Chem. Int. Ed. Engl. 20 (1981) No. 1
n
The crystals which separated from the crown arsane (6) fraction (32% of fraction) had a sharp melting point (106.5 " C )
and this led us to believe that only one product had been
formed.
The structures of the isolated compounds (l),(3), (5)-(7)
are consistent with the elemental analyses, and mass and 'HNMR spectral data (Table I).
U
Received: March 24, 1980 (2 668b IE]
German version: Angew. Chem. 93. 1 I7 ( I 98 1 )
I ) 2 PhAsHLi
2) 2 nBuLi
CAS Registry numbers:
( I ) . 75396-00-8; (2). 76124-37-3; [3), 76124-38-4 (4), 76135-99-4; (5). 76124-39-5;
(6). 76124-40-8; (71, 76124-4-9; PhAsLi2, 1073-41-2; PhAsHL,. 40965-94-4,
Br(CH2),CI, 109-70-6; Cl(CH2),C1, 142-28-9
sL i ph
F T hA m
s A
PhAs
A- ;$J(
s Li Ph
(4)
carried out in THF at 20°C unless otherwise stated)I5].Of
these, only the electrophiles (1) and (3) were isolated [(3);
yield 25% relative to (l)].In this connection it was advantageous that the arsane group reacted with alkyl halides much
less readily than the phosphane group.
Using the principle of dilution (all reactions carried out at
20°C in THF) oily fractions of the crown arsanes (5)-(7)I6l
were obtained from the starting materials and were cleaned
by passing through a chromatographic column (SO2: diethylether/pet. ether 1:20) and isolated by chromatography. Stereoisomeric mixtures were obtained; this also applied to (3).
111 K. Berghus, A . Hamsen, A. Rensing, A . Woltermann. Th. Kauffmann, Angew.
Chem. 93, 116 (1981): Angew. Chem. Int. Ed. Engl. 20, 117(1981).
121 Th. Kauflmann, J. Ennen, H. Lhotak, A. Rensing. F. Steinserfer. A. Wo'oNermann, Angew. Chem. 92. 321 (1980); Angew. Chem. Int. Ed Engl. 19, 328
(1980).
[3] L. Homer. H. Kunz, P. Walach, Phosphorus 6. 63 (1975); L. Homer, P. Walach, H . Kunz, Phosphorus Sulfur 5, 171 (1978): T A. DelDonno. W. Rosen, J
Am. Chem. SOC.99, 8051 (1977); Inorg. Chem. 17, 3714 (1978); E. P. Kyba.
C. W. Hudson, M . J. McPhaul. A. M. John, J. Am. Chem. SOC.99. 8053
(1977).
[4] A . Tzschach, J. Heinicke: Arsenheterocyclen. VEB Deutscher Verlag fur
Grundsroffindustrie, Leipzig 1978.
[5] For the preparation of PhAsLiH and PhAsLi2. see A. Tzschach. C Pucholke.
Chem. Ber. 97. 419 (1964).
[6] The yields of (5). (6), and 17) are calculated relative to ( 1 ) . the assumption being made that the formation of (2) from (I) as well as (4) from (3) is quantitative.
Alkyl(dicyclopentadieny1)lutetium Complexes:
Monomeric Alkyllanthanoid Derivatives'"'
(-,As
Ph'
As,)
u
'Ph
Table 1 . Physical data of the compounds obtained. 'H-NMR; &-valuesre]. TMS
in CDCI,. Mass spectra; 70 eV, m / e [a]
Cpd.
M.p.
or n
'H.N.M.R.
(1)
n::'=
7.23-7.68
3.33-3.71
1.75-2.12
1.5691
MS
(m: 5H),
(m; 4H),
(m; 8 H )
306 ( M + <
4.2%), 229 (IS), 189 (25),
187 (loo), 153 (19), 151 (19). 78
(19)
(3)
Oil [b]
7.12-7.68 (m: 15H), 617 ( M i -78, 37%), 425 (37), 423
3.34-3.65 (m; 4H),
(98), 311 (92), 227 (54), 187 (100),
1.53-2.12 (m: 20H)
119 (56), 117 (60)
(5)
011[bl
7.07-7.71
1.82-2.14
(m: 15H).
(m; 18H)
581 ( M i - 1, 2%), 539 (45). 505
(48). 463 (100). 346 (51). 311 (73,
227 (84)
16)
106.5"C
[cl
7.18-7.63
151-2.11
(m; 20H),
(m; 24H)
775 ( M +- 1 , 2%). 733 (29). 699
(17). 463 (30), 423 (33), 346 (74),
311 (71). 227 (100). 187 (48). 153
(76)
Oil [b]
7.13-7.53
1.35-2.17
(m; 30H).
(m; 36H)
1 164 (M 0.2%). 1122 (1), 969 (1).
811 (4), 617 (34). 423 (88). 403
(38). 227 (100). 187 (81). 153 (84)
(7)
+.
[a] For "CI-isotope. [b] Oily isomeric mixture. [c] From pet. ether (60-90
Angew. Chem. In(. Ed. Engl. 20 11981) No. 1
"C).
By Herbert Schumann, Worfgang Genthe, a&
Norbert Bruncks[']
Dedicated to Professor Wilhelm Klemm on the occasion
of his 85th birthday
Alkyl derivatives of lanthanoids of low coordination number are very unstable. Hitherto, the isolation of such derivatives at room temperature could be accomplished only with
sterically very demanding alkyl groups, with possible association via basic ligands or with formation of multinuclear
electron-deficient compounds"'. According to X-ray structure analysis the cyclopentadienyl(methy1)lanthanoid derivativesr2]first described in 1975 are dimeric with CH3 bridges
between two lanthanoid
We have now found that dicyclopentadienyllutetium chloride reacts with organolithium compounds in tetrahydrofuran at - 78 "C to give monomeric alkyl(dicyc1opentadieny1)lutetium derivatives, some of which are remarkably
thermostable. Whereas the methyl, ethyl and n-butyl derivatives can be detected only NMR spectroscopically in benzene
at room temperature as 1 :1 complexes with tetrahydrofuran
(THF) we have been able to isolate corresponding compounds with larger alkyl or aryl ligands as colorless to pale
yellow needles which are stable up to 100 "C (Table 1).
('1 Prof. Dr. H. Schumann, DipLChem. W. Genthe, DipLChem. N.
Bruncks
Institut fur Anorganische und Analytische Chemie der technischen Universitat Berlin
Strasse des 17. Iuni 135, D-1000 Berlin 12 (Germany)
["I
Organometallic Compounds of the Lanthanoids. Part 8. This work was supported by the Fonds der Chemischen Industrie and by the Senator fur Wirtschaft des Landes Berlin (ERP grant, Project 2327).-Part 7. H. Schumann.
G. M. Frisch, 2. Naturforsch. B 34, 748 (1979).
0 Verlag Chemie, GmbH. 6940 Weinheim, 1981
0570-0833/8~/0101~01l9 $ 02 50/0
119
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