An octahedral stannylmanganese stannylene complex1,2

Article abstract of DOI:10.1016/S0022-328X(98)00479-3

Treatment of decacarbonyldimanganese with the alkylarylstannylene RR′Sn (2), R=2,4,6-tBu₃C₆H₂, R′=CH₂C(CH₃)₂-3,5-tBu₂C₆H₃, furnishes the tetracarbonyl-stannylmanganese stannylene complex 3, in which the tin atom of the stannyl group is part of a stannaindan ring system. Reaction of 2 with [(OC)₂Fe(NO)₂] yields the tetrahedral iron stannylene complex [OC(NO)₂Fe=SnRR′] (4). The structures of 3 and 4 were determined by X-ray crystallography.

Full text of DOI:10.1016/S0022-328X(98)00479-3

Journal of Organometallic Chemistry 560 (1998) 125–129
An octahedral stannylmanganese stannylene complex1,2
Manfred Weidenbruch a,*, Artur Stilter a, Wolfgang Saak a, Karl Peters b,
Hans Georg von Schnering b
a Fachbereich Chemie der Uni6ersita¨t Oldenburg, Carl-6on-Ossietzky-Straße 9-11, D-26111 Oldenburg, Germany
b Max-Planck-Institut fu¨r Festko¨rperforschung, Heisenbergstraße 1, D-70506 Stuttgart, Germany
Received 24 November 1997
Abstract
Treatment of decacarbonyldimanganese with the alkylarylstannylene RR%Sn (2), R=2,4,6-tBu3C6H2, R%=CH2C(CH3)2-3,5-
tBu2C6H3, furnishes the tetracarbonyl-stannylmanganese stannylene complex 3, in which the tin atom of the stannyl group is part
of a stannaindan ring system. Reaction of 2 with [(OC)2Fe(NO)2] yields the tetrahedral iron stannylene complex [OC(NO)2Fe=
SnRR%] (4). The structures of 3 and 4 were determined by X-ray crystallography. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Manganese; Iron; Stannylene; Crystal structures
1. Introduction
lution (Scheme 1) [7]. Starting from the stannylene 2 we
have been able to synthesize the isotypical complexes
[(OC)5M=SnRR%], M=Cr, Mo, W [8,9] and to isolate
the compounds [(OC)4Fe=SnRR%] and [(OC)3Ni=
SnRR%]. However, because of its ready decomposition
in the crystal state it was not possible to obtain a
complete X-ray crystal structure of the tetrahedrally
coordinated nickel complex [10]. Characteristic features
of these complexes are long M–Sn bond lengths and
small C–Sn–C bond angles, indicating that the stan-
nylene 2 behaves mainly as a |-donor with only weak
y-acceptor properties. Accordingly, the stannylene oc-
cupies an axial position in the trigonal bipyramidal iron
complex [10] which, as predicted by theoretical calcula-
Although the first transition metal-stannylene com-
plex without donor stabilization, namely the compound
[(OC)5Cr=Sn{CH(SiMe3)2}2], was described more
than 20 years ago [2], the number of completely charac-
terized complexes of this type is still very small [3].
Thus, for example, reactions of tin(II) chloride with
various manganese complexes lead to compounds con-
taining the structural unit Mn–Sn–Mn in which, how-
ever, the tin atom achieves the coordination number 4
by means of either bridging halogen ligands or solvent
molecules [4,5]. One exception is the compound (v3-
Sn)[(p5-C5H4CH3)Mn(CO)2]3 prepared by Herrmann et
al. in which the naked tin atom has the coordination
number three and forms one short and two long bonds
to the three manganese atoms [6].
We recently succeeded in preparing the diarylstan-
nylene 1 which is stable in the solid state but undergoes
slow rearrangement to the alkylarylstannylene 2 in so-
* Corresponding author. Fax: +49 441 7983352.
1 See ref. [1].
2 Dedicated to Professor Heinrich No¨th on the occasion of his 70th
birthday.
Scheme 1.
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00479-3

126
M. Weidenbruch et al. / Journal of Organometallic Chemistry 560 (1998) 125–129
Fig. 1. Molecular structure of 3 in the crystal (hydrogen atoms omitted).
tions, is preferentially occupied by strong |-donor and
weak y-acceptor ligands [11].
The X-ray study confirmed the formation of the 18
electron complex 3 containing both a tri- and a tetra-
coordinated tin atom in trans-positions with the tin
atom of the stannyl group being incorporated in a
stannaindan ring system. The Sn–Mn–Sn bond angle
of 168.2(2)° is presumably attributable to the differing
coordination polyhedra of the two tin atoms. The two
Sn–Mn bond lengths differ appreciably [251.3(2) and
270.0(2) pm] and indicate the existence of one single
and one double bond. Although the Mn–Sn single
bond length correlates well with that of the reference
complex [(OC)5Mn–SnMe3] [d=267 pm] [12], the dou-
ble bond length is considerably larger than that of
244.5(1) pm determined by Herrmann et al. [6] and
again reflects the reduced y-acceptor capacity of 2 in
transition metal complexes. However, in spite of the
comparable covalent radii of chromium and man-
ganese, the value determined here is noticeably shorter
than that of 261.4(1) pm for [(OC)5CrSnRR%], a com-
pound with similar, octahedral coordination in which
In the present communication we report on the reac-
tion of decacarbonyldimanganese with 2, a reaction
following a different course to the previously described,
complex-forming processes, and on the formation of an
iron-stannylene complex with tetrahedral coordination.
2. Results and discussion
The reaction of excess 2 with decacarbonyldiman-
ganese proceeds with evolution of a gas and is complete
within a few hours. Work-up of the reaction mixture
results in the isolation of a pale yellow, crystalline
compound composed, according to its analytical data,
of one tetracarbonylmanganese fragment and two stan-
nylene units. Since a mononuclear manganese com-
pound with CO and the stannylene 2 as ligands should
possess an odd number of electrons, we attempted to
prove the presence of the unpaired electron by ESR
spectroscopy. However, the obtained spectrum indi-
cated the existence of a diamagnetic complex.
Table 1
Although the 1H- and 13C-NMR at first did not allow
any unequivocal conclusions to be drawn about the
structure of the obtained complex, the 119Sn-NMR
signals at 109 and 906 ppm demonstrated the presence
of one tri- and one tetra-coordinated tin atom in the
molecule. An X-ray crystallographic analysis (Fig. 1,
Table 1) not only confirmed the deductions from the
119Sn-NMR spectrum but also revealed some other
interesting features (Scheme 2).
Selected bond lengths (pm) and angles (°) for 3
MnꢀSn(1a)
MnꢀC(1)
Sn(1a)ꢀC(3a)
Sn(1a)ꢀC(30a)
Sn(1b)ꢀC(31b)
270.0(2) MnꢀSn(1b)
181.1(9) MnꢀC(2)
224.7(6) Sn(1a)ꢀC(21a)
224.7(6) Sn(1b)ꢀC(3b)
225.5(3)
251.3(2)
182.9(7)
219.4(3)
216.2(6)
Sn(1a)ꢀMnꢀSn(1b)
MnꢀSn(1b)ꢀC(3b)
168.4(2) C(3b)ꢀSn(1b)ꢀC(21b)
118.8(2) MnꢀSn(1b)ꢀC(21b)
113.3(2)
127.8(1)

M. Weidenbruch et al. / Journal of Organometallic Chemistry 560 (1998) 125–129
127
Scheme 2.
the bond is markedly lengthened. In harmony with this
observation, the trigonal bipyramidally coordinated tin
atom in 3 exhibits an appreciably widened C–Sn–C
angle of 113.2(2)° in comparison to a value of merely
91.2(2)° in the chromium compound.
Fig. 2. Molecular structure of 4 in the crystal (hydrogen atoms
omitted).
The formation of the manganese complex 3 from
[(OC)10Mn2] and 2 can be interpreted most simply in
terms of a primary insertion of 2 into the Mn–Mn
bond with subsequent cleavage of one of the ortho-tert-
butyl methyl CH bonds to form the stannyl group
under elimination of [HMn(CO)5]. Indeed, the 1H-
NMR spectrum of the volatile reaction products did
show a signal at −6.9 ppm that is characteristic for a
hydrogen atom attached to a manganese carbonyl frag-
ment. Final substitution of a CO ligand by 2 then
furnishes the isolated product.
In order to obtain, in addition to the octahedrally
and trigonal bipyramidally coordinated transition metal
complexes, a completely characterizable complex with a
tetrahedral arrangement containing 2 as a ligand, stan-
nylene 2 was allowed to react with [(OC)2Fe(NO)2] in a
1:1 molar ratio. The dark red, crystalline compound 4
was isolated in 77% yield and its 119Sn-NMR signal at
1006 ppm is indicative of the formation of a stannylene
complex.
An X-ray crystallographic analysis of 4 (Fig. 2, Table
2) revealed a distorted tetrahedral iron-stannylene com-
plex with an Fe–Sn bond length of 248.4(1) pm. This
length is somewhat shorter than those of the single
bonds in similarly substituted stannyl componds (values
between 260 and 270 pm) and thus indicative of multi-
ple bond character [13,14]. It is interesting to note that
the value determined here is almost identical with the
Fe–Sn bond length of 248.8(1) pm in the complex
[(OC)4FeSnRR%] [10] in spite of the incorporation of 2
into different polyhedra.
3. Experimental section
3.1. General procedure
All reactions were carried out in oven-dried glass-
ware under an atmosphere of dry argon.
1
The H-, 13C-, and 119Sn-NMR spectra were obtained
on a Bruker AM 300 spectrometer using C6D6 as
solvent. IR spectra were taken on a Bio-Rad FTS-7
spectrometer. Mass spectra were recorded on a Varian-
MAT 212 instrument. Elemental analyses were per-
formed by Analytische Laboratorien, D-51779 Lindlar,
Germany.
3.2. Formation of the tetracarbonylstannylmanganese
stannylene complex (3)
At 35°C a solution of 2 (1.10 g, 1.80 mmol) in 20 ml
of THF was added to a solution of [Mn2(CO)10] (0.30 g,
0.77 mmol) in 20 ml of THF over a period of 2 h. To
Table 2
Selected bond lengths (pm) and angles (°) for 4
FeꢀSn
FeꢀN(39)
SnꢀC(1)
248.4(1)
165.7(5)
218.1(5)
FeꢀN(38)
FeꢀC(37)
SnꢀC(9)
165.9(5)
179.1(8)
219.2(4)
C(1)ꢀSnꢀC(9)
FeꢀSnꢀC(1)
100.5(2)
132.5(1)
FeꢀSnꢀC(9)
127.0(1)

128
M. Weidenbruch et al. / Journal of Organometallic Chemistry 560 (1998) 125–129
Table 3
complete the reaction, the mixture was stirred for an
additional 3 h at this temperature. The mixture was
filtered and the solvent removed. Recrystallization of the
residue from 10 ml of DME at −24°C yielded 0.69 g
(65% yield) of pale yellow crystals of 3, m.p. 178°C.
1H-NMR: l 1.24 (s, 9 H), 1.25 (s, 9 H), 1.27 (s, 18 H),
1.29 (s, 18 H), 1.35 (s, 18 H), 1.43 (s, 3 H), 1.47 (s, 3 H),
1.53 (s, 3 H), 1.59 (s, 6 H), 1.61 (s, 3 H), 1.80 (s, 9 H),
2.15 (s, 2 H), 2.46 (s, 2 H), 2.65 (AB-system, 2 H,
Crystallographic data for 3 and 4
3
4
Empirical formula
C76H115MnO4Sn2 C37H58FeN2O3Sn·
C7H8
1385.00
Molar mass
Unit cell dimenstions
a (pm)
b (pm)
c (pm)
h (°)
845.88
989.0(1)
1421.4(2)
1470.3(1)
94.11(1)
98.02(1)
110.07(1)
1906.4(4)
1
917.34(5)
1179.26(7)
2166.3(1)
89.904(5)
83.017(5)
82.118(5)
2303.9(2)
2
4
2J=13.1 Hz), 7.37 (m, 3 H), 7.42 (t, 1 H, J=1.7 Hz),
4
7.44 (s, 2 H), 7.45 (d, 2 H, J=1.6 Hz), 7.66 (d, 2 H,
i (°)
k (°)
4J=1.7 Hz) ppm. 13C-NMR: l 31.29 (Cp), 31.86 (Cp),
32.93 (Cp), 33.54 (Cp), 33.77 (Cp), 34.18 (Cp), 34.84 (Cp),
35.46 Cp), 37.35 (Cq), 37.56 (Cq), 38.48 (Cq), 39.04 (Cq),
39.91 (Cq), 40.20 (Cq), 45.39 (CH2), 59.14 (CH2), 119.30
(CH), 119.49 (CH), 119.88 (CH), 120.69 (CH), 122.41
(CH), 123.82 (CH), 125.65 (CH), 137.43 (Cq), 149.44
(Cq), 150.07 (Cq), 150.62 (Cq), 150.96 (Cq), 155.86 (Cq),
156.31 (Cq), 160.69 (Cq), 203.62 (CO), 221.83 (CO) ppm.
Cp and Cq refer to primary and quaternary carbon atoms
respectively. 119Sn{1H}-NMR: l 108 (broad), 960
(broad) ppm. IR (KBr) w: 1935, 1925 (CO) cm−1. MS
(CI, isobutane): m/z 1386 (MH+, 6%). Anal. Found: C,
65.66; H, 8.12. C76H115MnO4Sn2 (1385.06) calc.: C,
65.90; H, 8.37%.
V (×106) (pm3)
Z
Dcalcd (g cm−3
Crystal system
Space group
)
1.206
Triclinic
P1
1.219
Triclinic
P1
Crystal size (mm3)
Data collection mode
2qmax (°)
0.38×0.38×0.15 0.5×0.55×0.2
ꢀ-2q-scan
48
6250
5963
ꢀ-scan
55
12 551
10 567
No. of reflections
No. of unique reflections
No. of observed reflec-
tions
4880 (I\2|(I))
9285 (F\3|(F))
Linear abs. coefficient
0.37
0.89
(mm−1
)
Data to parameter ratio
R, (Rw)
wR2 (all data)
16.78
0.060
0.160
21.80
0.061 (0.064)
—
3.3. Formation of the carbonyldinitrosyliron stannylene
complex (4)
Residual electron density
0.673 and −0.344 0.88 and −0.94
−3
˚
(e A
)
At −50°C a solution of [(OC)2Fe(NO)2] (0.27 g, 1.69
mmol) in 50 ml of toluene was added dropwise to a
solution of 2 (1.03 g, 1.69 mmol) in 50 ml of toluene. To
complete the reaction, the resulting mixture was stirred
for 18 h at r.t. The solution was concentrated to a volume
of 10 ml. After the addition of 10 ml of n-hexane, the
solution was cooled to −50 °C. After 3 days at this
temperature rhombohedral, dark red crystals of 4 were
obtained. Yield: 0.98 g (77%), m.p. 111–112°C. 1H-
NMR: l 1.23 (s, 18 H), 1.29 (s, 9 H), 1.37 (s, 18 H), 1.55
lizes with a molecule of toluene. In each case, the
crystal was mounted in a thin-walled glass capillary.
Data collection was performed at 296(2) K on a
Siemens STOE AED 2 (3) or a Siemens P4 diffrac-
tometer (4) using graphite-monochromated Mo–Kh
radiation.
The structures were solved by direct phase determi-
nation using the SHELX’s program systems and
refined by full-matrix least-squares techniques against
F2 (3) or F (4) with the SHELXL 93 [15] or
SHELXTL PLUS program systems. Hydrogen atoms
were placed in calculated positions, and all other
atoms were refined anisotropically.
4
(s, 6 H), 2.04 (s, 2 H), 7.37 (d, 2 H, J=1.65 Hz), 7.44
(t, 1 H), 7.47 (s, 2 H) ppm. 13C-NMR: l 31.37 (Cp), 31.72
(Cp), 33.14 (Cp), 35.19 (Cq), 38.91 (Cq), 39.20 (Cq), 57.77
(CH2), 119.51 (CH), 121.08 (CH), 122.96 (CH), 125.64
(CH), 149.06 (Cq), 149.97 (Cq), 150.50 (Cq), 150.83 (Cq),
156.26 (Cq), 223.59 (CO) ppm. 119Sn-NMR: l 1006 ppm.
IR (KBr) w: 1983 (s) (CO), 1748 (s), 1707 (s) (NO) cm-1.
MS (CI, isobutane): m/z 755 (MH+, 100%). UV–vis:
umax(m) 280 (broad, tailing off into the visible region)
(9000) nm. Anal. Found: C, 58.85; H, 7.88; N, 3.76.
C37H58FeN2O3Sn (753.44) calc.: C, 58.98; H, 7.76; N,
3.72%.
The molecules of 3 are chiral with an Sn–Mn–Sn
angle of 168.4(2)°. Owing to racemic twinning an in-
version center is observed so that the space group P1
(
results [1].
Acknowledgements
3.4. X-ray structure analyses of 3 and 4
Financial support of our work from the Deutsche
Forschungsgemeinschaft and the Fonds der Chemi-
schen Industrie is gratefully acknowledged.
Crystal and numerical data of the structure deter-
minations are given in Table 3. Compound 4 crystal-

M. Weidenbruch et al. / Journal of Organometallic Chemistry 560 (1998) 125–129
Angew. Chem. Int. Ed. Engl. 33 (1994) 1846.
129
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