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Synthesis and Structure of the Tetradecker Complex Bis(tricarbonylmanganese- -thiadiborolene)iron.

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and have found that, depending upon the nature of the reagents
and conditions used (solvent, temperature), all the possible
reaction routes A, B, C and/or D outlined in Scheme 1 can
be observed. Some of these reactions are of synthetic value.
When phenyl vinyl selenide ( I ) is allowed to react with
n-butyllithium in tetrahydrofuran (THF) for 1 h at -78"C,
and heptanal is then added, butyl vinyl selenide (2) (70%) and
1-phenyl-1-heptanol(3) (68 %y21 are formed via route A. Small
amounts of hexyl phenyl selenide ( 4 ) ( 5 %) and 2-phenylseleno-1-nonen-3-01 (6) (17 %) are also formed, via addition
(route B) and metalation (route C), respectively. When the
reaction is performed at -30 to 0°C the yield of addition
product ( 4 ) increases (- 10°C: 28 %) and that of the cleavage
product decreases (- 10°C: 18 %).
When THF is replaced by diethyl ether, route B largely
predominates; if the reaction is conducted at 20°C for 5 min
before quenching with water, ( 4 ) is obtained in 65 % yieldc3].
With longer reaction times the yield of ( 4 ) drops considerably
(30min: 30 %). The accompanying side-products were not
identifiedl4.'I. On addition of heptanal after 5 minutes reaction
time at 2 0 T , 40 % of the corresponding 6-phenylseleno-7-tridecanol (5) is formed along with 10% of ( 4 ) (route B).
(2) (13 %) and (3) (20 %) (via route A) as well as ( 6 ) (20 %)
(via route C) are also obtained.
Lithium diisopropylamide (LDA) is found to be the most
effective reagent for metalation of the title compound: no
C-Se cleavage was observed with this reagent16! However,
depending on the nature of the solvent, elimination (route
D) can occur as well as metalation (route C). For example,
reaction of ( I ) and 1.5 equivalents LDA at -78°C for one
hour furnishes a carbanion, which can be trapped with D 2 0
in 80 % yield as 1-deuteriovinyl phenyl selenide and with
heptanal in 40 % yield as 2-phenylseleno-t-nonen-3-01
(6).
In hexamethylphosphoric triamide (HMPT)/THF (1 :20,
-78"C, 1 h)"] the alkylation is even more strongly favored.
Addition of one equivalent of decyl bromide (-78 "C, 2 h)
leads to 2-phenylseleno-I-dodecene(7) (70 %) (route C) and
decyl phenyl selenide (8) (23 %) (route D). In HMPT/THF
(1 : 3) the elimination reaction predominates; the selenide (8)
is formed in 65 % yield.
( 4 ) + CHSI
Nal
DMF
Bu-CH2-CH2-I
[3] A solution of ( I ) (1 mmol) in ether (2nd) is treated at 20°C under
argon with 1 mmol n-butyllithium and the mixture stirred for 1 h. After
hydrolysis the mixture is extracted with ether and the extract dried.
Distillation of the crude product affords pure ( 4 ) , b.p. 7O"C/O.I torr,
identical with an authentic sample.
[4] During the completion of our work a short communication appeared,
dealing in part with the reaction of ( I ) with n-butyllithium: Th. Kauflmann, H . Ahlers, H . J . Tilhard, A . Woltermann, Angew. Chem. 89, 760
(1977); Angew. Chem. Int. Ed. Engl. 16,710(1977).
[5] If the reaction mixture is stirred for a longer time the initially formed
rr-selenocarbanion rearranges; as in the case of the analogous sulfur
compounds, ring-metalated derivatives are formed. With C H d , a mixture
of hexyl tolyl selenides is obtained: with heptanol, no P-selenoalcohol
( 5 ) is formed, but instead a mixture of 1-tolyl-1-hexanols is obtained.
(75 %,)from 1.1-bis(meth[6] a)Synthesis of I-lithio-1-methylseleno-1-octene
ylseleno)-1-octene by C -Se cleavage: A. Krief, lecture at Rouen (France),
July 3, 1977; b) Synthesis of P-lithio-P-phenylselenostyrene by C-Se
cleavage: 5. T: Grobel, D. Seebach, Chem. Ber. 110, 867 (1977).
[7] A solution of LDA (3mmol) in T H F (3ml) is treated with 2mmol
( I ) in HMPT/THF (1 :9) at -78°C and the mixture stirred for 1 h.
After addition of 2mmol decyl bromide in T H F ( 3 r d ) the reaction
mixture is stirred for 2h, hydrolyzed, extracted with ether, and the
extract dried. The crude product is purified by preparative thick layer
chromatography ( S O 2 , (Merck) 2 mm, pentane, Rf =0.62).
181 M. Sevrin, W Dumont, L. Heuesi, A . Krief, Tetrahedron Lett. 1976,
2647; D . Labar, W Dumont, L. Heuesi, A. Krief, ibid., in press.
[9] A . Burton, L. Heuesi, A. Krief, unpublished results.
Synthesis and Structure of the Tetradecker Complex
Bis(tricarbonylmanganese-CL,rl-thiadiborolene)iron[
By Walter Siebert, Christian Bohle, Curl Kriiger, and K-Hung
Tsuy~l
The possibility of constructing oligo-decker and poly-decker
complexes (quadruple-decker['"], multiple-decked stacked
compounds[2b1)has already received consideration. We have
extended our studies on Lewis acid ligands in sandwich and
triple-decker complexes[31to tetradecker complexes and now
wish to report the first trinuclear complex ( 4 ) containing
two bridging thiadihorolene and six terminal carbon monoxide
ligands.
11>(
HC2H5
2Xc-
H3C-B,
(9)
S
,B-CH,
Fe
Received: March 30, 1978 [Z 982 IE]
German version: Angew. Chem. 90, 550 (1978)
CAS Registry numbers:
( I ) , 35167-28-3; (2). 66769-95-7: ( 3 ) , 614-54-0; ( 4 ) , 63866-88-6; (S), 6676994-6; (6), 66769-93-5; (7). 66769-92-4; ( 8 ) , 61539-89-7; (9), 638-45-9; (JO),
592-41-6
[l] W Dumonf, P . Bayet, A. Kriej; Angew. Chem. 86, 857 (1974); Angew.
Chem. Int. Ed. Engl. 13, 804 (1974); D. Seebach, A . K . Beck, ibid. 86,
859 (1974) bzw. 13, 806 (1974).
[2] To a solution of ( I ) (1 mmol) in T H F (2ml) is added n-butyllithium
(1 mmol) at -78°C under argon and the mixture stirred for one hour.
After slow addition of 1 mmol heptanal in T H F (2nd) the solution
is allowed to stand for 2 b at -78°C and 1 h at 2 5 T , hydrolyzed,
and worked up in the usual way.
Angew. Chem. Int. Ed. Engl. 17 (1978) No. 7
Mn
Fe
Mn
-B@- S
We have used the hexyl phenyl selenide ( 4 ) obtained via
route B for the synthesis of hexyl iodide (9) and 1-hexene
(10) (80 % and 74 % yield, resp.)[']. 2-Phenylseleno-I-dodecene (7) can be readily hydrolyzed to 2-dodecanone (91 %
yield)['].
(C0)3
1-7
(4)
B ( 3 B'S'
Mn
Simultaneous reaction of the thiadiborolene derivative
with MnZ(C0)' and [(C5H5)Fe(C0)2]2gives the green
air-stable triple-decker complex (2), m.p. 194"C ['H-NMR:
6=3.85 (s, 5), 3.0-2.1 (m, 4), 1.53 (s, 6), 1.36 (t, 6) in CSz
rel. to TMS int.; "B-NMR: 6 = 18.0 in CS2 rel. to Etz0.BF3
ext.; IR: v(C0)=2031 (s), 1946 (s), 1935 (s) cm-' in C2C14;
MS: M + (14), (M-3CO)' (IOO), {(C5HS)FeL)+(9), ...]. A
first example of this triple-decker type of complex containing
dzferent terminal ligands, viz. [(C5H5)Co(C2B3)Fe(CO)3],
has
recently been described[5!
(Z)'4a1
[*I
Prof. Dr. W. Siebert, Dipl.-Chem. C. Bohle
Fachbereich Chemie der Universitat
Lahnberge, D-3550 Marburg 1 (Germany)
Dr. C. Kriiger, Dr. Y.-H. Tsay
Max-Planck-Institut fur Kohlenforschung
Lembkestrasse 5, D-4330 Miilheim-Ruhr 1 (Germany)
527
As in ferrocene, the C5H5 ligand of (2) can be replaced
with c6H6/AICl3to give the red-violet triple-decker salt (3)
which is sensitive to hydrolysis. Its thermolysis at 14O0C/O.1
torr affords a low yield of the orange-red tetradecker complex
( 4 ) , m.p.: dark coloration above 155"C, decomposition at
210°C:
2 [(CsHs)Fe.(l).Mn(C0)3]0AlC1,0
(3)
(4)
+
2
2 CsHtj + [FeClZ, 2 A l C l S ]
The IR spectrum of ( 4 ) contains three strong bands at
2033, 1955, and 1944cm-' (in C2C14) showing a significant
shift relative to the C O stretching vibrations of the tripledecker [(C0)3Mn.(Z).Mn(C0)3] (2021, 1966, 1956cm-', in
C Z C ~ ~ )The
[~F
~D
] .mass spectrum exhibits an isotopic pattern
for the molecular ion [(C0)3MnL]2Fe+ [L=(l)] (Irel=100
based on "B4) which is due to the presence of four boron
atoms. Apart from M' (12), the following principal fragments
are observed at 70eV: {M-3CO}+ (50), {Mn2L2Fe}+(16),
{MnLFe-28)" (8),MnL+(4),L+(12),(C2H5)2C2BCH:(100).
The structure of the complex ( 4 ) is confirmed by X-ray
structure analysisE6].Both of the independent molecules in
the triclinic unit cell have a center of inversion (Fe); they
differ in the conformation of the substituents on the planar
(kO.01x 10-I0m) CzB2Srings. Owing to the center of inversion these rings have a mutual transoid arrangement whereas
they are staggered (each rotated 90") in the comparable tripledecker sandwich (C2B2S)3C02[71.The bond lengths of the
bifacially coordinated ring atoms are lengthened in a typical
manner relative to the corresponding distances in unifacially
coordinated C2B2S ringsL8](average values: B-S 1.928(7),
B-C 1.544(9), C-C (1.477(9)). The F c M n distances are
3.408(1) and 3.391(1) 10-"m.
We attribute this first example of trans orientation of neighboring CzBzS rings to formation of two #-electron systems
in the central (C2B2S)2Fe sandwich. Two equivalent
approaches can be adopted in describing the bonding in ( 4 ) .
According to the x6/d6-8
( 4 ) is the first member
of the tetradecker family with 42-48 valence electrons; four
planes of ligands (two C2B2S rings as #-electron donors
and two (CO), groups as 06-electron donors) are held together
by three d6 metal ions. According to the closo approach[gb],
( 4 ) can be regarded as a double cluster of two pentagonal
bipyramids with a common Fe apex; 2 n + 2 = 16 skeletal electrons are necessary to hold the C2B2SMnFeclusters together;
they are provided by C(2 x 3), B(2 x 2), S(4), Mn(l), and Fe( 1).
Procedure
A mixture of ( I ) (0.85g, 5.12mmol), Mn2(CO)lo (1.49g,
3.84mmol) and [C5H5Fe(C0)2]2(1.35g, 3.84mmol) in 20ml
mesitylene is heated under nitrogen for 0.5h at 165°C. After
removal of solvent the residue is taken up in hexane and
chromatographed on dry silica gel (Woelm 100-200). The
first
band
contains
Mn2(CO)lo
and
some
[(C0)3Mn.(l ).Mn(C0)3], the second band green (2) (0.82 g;
best yield in analogous reactions 37 %).
A mixture of (2) (0.25g, 0.58mmol) and AlC13 (0.25g,
1.87mmol) in benzene (20ml) is stirred under nitrogen for
0.5 h at 90°C. Reddish-violet (3) precipitates out. On heating
(3) (0.2 g, 0.33 mol) to 140-16OoC/0.1 torr a yellow-brown
sublimate is obtained, which on recrystallization from CS2
affords orange-red crystals; yield 3 mg (2.7 %).
Received: April 25, 1978 [Z 991 IE]
German version: Angew. Chem. YO, 558 (1978)
CAS Registry numbers:
( I ) , 54677-51-9; ( 2 ) , 66921-71-9; ( 3 ) , 66984-57-4; ( 4 ) . 66921-70-8;
Mn2(CO),o,10170-69-1; [(CSHS)Fe(C0)2]2,12154-95-9
Tetradecker Complexes, Part 1. This work was supported by the Deutsche
Forschungsgemeinschaft and the Fonds der Chemischen Industrie.
a) H . Werner, Angew. Chem. 89, 1 (1977); Angew. Chem. Int. Ed. Engl.
16, 1 (1977); b) D. C . Beer, !I R . Miller, L. G . Sneddon, R . N . Grimes,
M . Mathew, G . J . Palenik, J. Am. Chem. Soc. 95, 3046 (1973).
W. Sirbert, Nachr. Chem. Tech. Lab. 25, 597 (1977); W Siebert, M .
Bochmann, Angew. Chem. 89, 895 (1977); Angew. Chem. Int. Ed. Engl.
16, 857 (1977).
a) W Siebert, R . Full, J . Edwirr, K . Kinberger, Chem. Ber. I l l , 823
(1978); b) W S i e b e r t , K . Kinberger, Angew. Chem. 88,451 (1976); Angew.
Chem. Int. Ed. Engl. 1 5 , 434 (1976).
W M . Maxwell, !l R . Miller, R . N . Grimes, Inorg. Chem. 15, 1343
( I 976).
Crystal data: a=9.679(2), h = 12.286(2), c = 13.364(3) (all values in lo-''
m), r=113.38(2), 8=97.61(2), ;.=80.08(1)", space group Pi, Z = 2 ,
dber=1.539g.cm-'; 4986 reflections, 1150 unobserved; R = 0 . 0 4 6 .
C. Kruger, J . C. Sekutowski, unpublished.
W Siebert, 7: Renk, K . Kinberger, M . Bochmann, C . Kriiger, Angew.
Chem. 88, 850 (1976); Angew. Chem. Int. Ed. Engl. 15, 779 (1976);
W Siebert, R . Full, J . Edwin, K . Kinberger, C. Kriiger, J. Organomet.
Chem. 131, l(1977).
a) J . W Lauher, M . Elian, R. H . Summerville, R . HoJfmann, J. Am.
Chem. SOC.98,3219 (1976); b) K. Wade. Adv. Inorg. Chem. Radiochem.
18, 1 (1976).
4-Alkoxy-1-phenylphosphacyclohexadiene+ 1-Alkoxy1-phenyl-31 5-phosphorin Rearrangement
By Gottfried Markl, Rainer Liebl, and Alois Hiittner[*]
4-Alkyl- or 4-aryl substituted 1-aryl-4-methoxy-l-arsa-2,5cyclohexadienes ( 1 ) undergo H+-catalyzed rearrangement to
2-aryI-h3-arsenins ( 2 ) ['!
[*] Prof. Dr. G. Markl, Dipl.-Chem. R. Liehl, A. Hiittner
Fig. 1. Molecular structure of complex ( 4 ) in the crystalline state
528
Chemisches lnstitut der Universitat
Universitatsstrasse 31, D-8400 Regenshurg 1 (Germany)
Angew. Chem. Int. Ed. Engl. 17 (1978) N o . 7
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tetradecker, structure, complex, synthesis, thiadiborolen, iron, bis, tricarbonylmanganese
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