5208 Organometallics, Vol. 17, No. 23, 1998
Notes
Ta ble 1. Cr ysta llogr a p h ic Da ta for 6 a n d 7
Sch em e 4a
6
7
empirical formula
fw
C
37H58S2Sn
C38H58S4Sn
761.85
34.624(3)
9.922(1)
11.700(1)
90
101.408(6)
90
3940.1(5)
4
685.64
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
14.327(2)
15.644(2)
18.568(2)
112.112(14)
104.402(15)
95.141(15)
3655.7(8)
4
D(calcd) (g cm-3
cryst size (mm)
cryst syst
)
1.246
1.248
0.52 × 0.27 × 0.26 0.3 × 0.2 × 0.2
triclinic
monoclinic
C2/c
ω-scan
55
4869
4527
0.88
19.27
space group
data collection mode
2θmax (deg)
P1h
then be responsible for the formation of the double
insertion product 7 (Scheme 4). A point in favor of this
proposal is the weakness of the Sn-C bonds in 1, which
is otherwise reflected in the always occurring rear-
rangement to 2. However, this process is hindered by
the addition of CS2 while concomitantly the labile Sn-C
bond, unlike the stannylene 3, makes the observed
migration of the aryl group to the CS2, carbon atom.
52
no. of rflns measd
no. of unique rflns
31 389
13 175
0.835
18.27
0.0363
0.0905
lin abs coeff (mm-1
)
data-to-parameter ratio
R [I > 2σ(I)]
wR2 (all data)
0.038
0.039 (Rw)
430, -620
residual electron density 961, -1065
(e nm-3
)
disulfide (4.0 mL, 67 mmol) in 60 mL of toluene was heated
at 60 °C for 6 days with stirring. After this time all volatile
compounds were distilled off. The residue was redissolved in
60 mL of toluene and insoluble material filtered off. Concen-
tration of the solution to a volume of 40 mL and cooling at 4
°C afforded 2.0 g (40% yield) of orange crystals of 7, mp 248
Exp er im en ta l Section
Gen er a l P r oced u r e. All manipulations were carried out
in oven-dried glassware under an atmosphere of dry argon.
The 1H, 13C, and 119Sn NMR spectra were obtained on a Bruker
AM 300 spectrometer using C6D6 as solvent. UV/vis spectra
were taken on a ConSpec spectrometer with fiber optics.
Elemental analyses were performed by Analytische Labora-
torien, D-51779 Lindlar, Germany. Stannylene 1 was prepared
according to the literature procedure.3,12
°C: 1H NMR δ 1.28 (s, 18 H), 1.70 (s, 36 H), 7.61 (s, 4 H); 13
C
NMR δ 31.35 (Cp), 34.25 (Cp), 35.04 (Cq), 39.27 (Cq), 123.86
(CH), 145.05 (Cq), 147.24 (Cq), 149.77 (Cq), 259.23 (CS2); 119Sn
NMR δ 56.3; UV/vis λmax(ꢀ) 364 (9700), 464 (1080) nm. Anal.
Calcd for C38H58S4Sn: C, 59.91; H, 7.67; S, 16.83. Found: C,
60.06; H, 7.84; S, 16.69.
Cr ysta llogr a p h ic An a lyses. Crystal and numerical data
of the structure determinations are given in Table 1. Single
crystals were grown from saturated solutions in toluene at 4
°C. Data were collected on a STOE IPDS diffractometer at 213
K (6) or a Siemens P4 diffractometer (7) at 296 K using
graphite-monochromated Mo KR radiation (0.710 73 Å). The
structures were solved by direct phase determination against
F2 (6) or F (7) with the SHELX 9313 or SHELXTL program
systems and refined by full-matrix least-squares techniques.
Hydrogen atoms were placed in the calculated positions, and
all other atoms were refined anisotropically.
2,4,6-Tr i-ter t-bu t ylp h en yllt in (II) 2,4,6-Tr i-ter t-b u t yl-
ben zen ed ith ioca r boxyla te (6). To the dark red solution of
1 (4.0 g, 6.6 mmol) in 60 mL of toluene was added carbon
disulfide (4.0 mL, 67 mmol, large excess), and the mixture was
heated at 60 °C for 3 days with stirring. After this time all
volatile compounds were distilled off. The residue was redis-
solved in 60 mL of toluene and insoluble material filtered off.
Concentration of the solution to a volume of 40 mL and cooling
at 4 °C provided 2.4 g (51% yield) of a crude product which
consisted of a 2:1 mixture of pure crystals of 6 and 7. Manual
selection furnished 1.6 g (34%) of light red crystals of 6, mp
225 °C: 1H NMR δ 1.23 (s, 9 H), 1.35 (s, 9 H), 1.47 (s, 18 H),
1.50 (s, 18 H), 7.45 (s, 2 H), 7.52 (s, 2 H); 13C NMR δ 31.33
(Cp), 31.60 (Cp), 33.40 (Cp), 33.93 (Cp), 34.62 (Cq), 35.00 (Cq),
39.04 (Cq), 41.03 (Cq), 123.25 (CH), 123.59 (CH), 145.29 (Cq),
146.57 (Cq), 148.77 (Cq), 149.61 (Cq), 151.88 (Cq), 159.12 (Cq),
253.28 (CS2) (Cp and Cq refer to primary and quaternary
carbon atoms); 119Sn NMR δ 652.0; UV/vis λmax(ꢀ) 466 (1530
nm). Anal. Calcd for C37H58S2Sn: C, 64.81; H, 8.52; S, 9.35.
Found: C, 64.65; H, 8.59; S, 9.40. Fraction 2 (0.8 g, 17%) was
identified as the 2-fold insertion product 7 (see below).
Tin (II) Bis(2,4,6-tr i-ter t-bu tylben zen ed ith ioca r boxy-
la te) (7). A dark red solution of 1 (4.0 g, 6.6 mmol) and carbon
Ack n ow led gm en t. Financial support of our work
by the Deutsche Forschungsgemeinschaft and the Fonds
der Chemischen Industrie is gratefully acknowledged.
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal
data, atomic coordinates for H atoms, bond lengths, bond
angles, and anisotropic displacement coefficients for 6 and 7
(12 pages). Ordering information is given on any current
masthead page.
OM980552E
(12) Auner, N.; Klingebiel, U. In Herrmann-Brauer: Synthetic
Methods of Organometallic and Inorganic Chemistry; Herrmann, W.
A., Ed.; Thieme Verlag: Stuttgart, Germany, 1996; Vol. 2, p 288.
(13) Sheldrick, G. M. SHELX 93. Program for crystal structure
refinement; Universita¨t Go¨ttingen: Go¨ttingen, Germany, 1993.