Ruthenacyclopentenyl Complexes
Organometallics, Vol. 15, No. 3, 1996 973
solution of 3 (126 mg, 0.130 mmol) was added ButNC (74 µL,
0.65 mmol), and the mixture was stirred at 80 °C for 12 h.
The volatile materials were removed in vacuo, and the result-
ing solid was crystallized from toluene-MeOH to give 5‚1/
2C7H8 as green crystals (115 mg, 80%). IR (KBr): ν(CN) 2062
3 a n d 4. The orientation matrices and unit cell parameters
were derived from a least-squares fit of 25 machine-centered
reflections with 2θ values between 20 and 25°. Three check
reflections measured every 100 reflections showed no signifi-
cant decay during data collection. All calculations were
performed by using the UNIX-III program package at the
computer center of The University of Tokyo.20 The Ru atoms
were found by the direct-methods programs MULTAN (for 3)
or SHELXS-8621 (for 4). Subsequent cycles of block-diagonal
least-squares refinements and difference Fourier maps re-
vealed all non-hydrogen atoms, which were refined anisotro-
pically. Hydrogen atoms were not included in the structure
factor calculations of 3 and 4.
cm-1 1H NMR (C6D6, 400 MHz): δ 8.02, 6.81 (d, 2H J ) 7.9
.
Hz, aryl), 7.50, 7.46, 7.37, 7.35, (d, 1H each, J ) 7.9 Hz, aryl),
7.11 (m, 4H, aryl), 6.46, 5.57, 2.30 (s, 1H each, η1:η2-µ-C(Tol)d
CHaC{C(Tol)dCHbSPri}dCHcTol, Hb, and Hc), 2.99, 2.55 (br
s, 1H each, SCHMe2), 2.47, 2.11, 1.96 (s, 3H each, C6H4Me),
1.97, 1.54 (s, 15H each, C5Me5), 1.32, 1.28, 1.15, 1.00 (d, 3H
each, J ) 6.7 Hz, SCHMe2), 1.09 (s, 9H, But). Anal. Calcd for
C
61.5H81NS2Ru2: C, 67.12; H, 7.42; N, 1.27. Found: C, 66.47;
H, 7.53; N, 1.31.
5‚1/2C7H8 a n d 6. Cell constants and orientation matrices
for data collection were obtained from a least-squares fit of
25 machine centered reflections in the range 27 < 2θ < 33°
for 5‚1/2C7H8 or 39 < 2θ < 40° for 6. The intensities of three
representative reflections were measured every 150 reflections,
for which no significant decay was observed during data
collection. Structure solution and refinements were performed
by using the TEXSAN crystallographic software package.22 The
structures were solved by a combination of Patterson methods
and Fourier techniques and refined by the use of full-matrix
least-squares techniques. Hydrogen atoms were placed at the
calculated positions and included in the refinements with fixed
parameters. In the structure refinements of 5‚1/2C7H8, two
methyl carbon atoms attached to C(31) in the SPri group were
placed at the three disordered positions and refined as C(32),
C(33), and C(34) with 75%, 75%, and 50% occupancies,
respectively. In the final stages of the structure solution of
5‚1/2C7H8, three peaks were found in a difference Fourier map,
which were assignable to the three independent ring carbon
atoms in the toluene molecule packed at the crystallographic
inversion center. However, isotropic refinements attempted
for these three carbon atoms resulted in the increased distor-
tion of the benzene core. Therefore these were not refined and
included in the structure refinements as fixed contributors.
The benzylic carbon atom in this toluene molecule could not
be placed due to the high degree of disorder. Hydrogen atoms
in the solvating toluene and that attached to C(31) in the
disordered Pri group were not included in the refinements of
the structure for 5‚1/2C7H8.
Rea ction of Din u clea r Meta lla cycle 4 w ith Bu tNC To
F or m Dir u th en iu m Com p lex 6. To a toluene (7 mL)
solution of 4 (162 mg, 0.194 mmol) was added ButNC (110 µL,
0.973 mmol), and the mixture was stirred at 80 °C for 12 h.
The volatile materials were removed in vacuo, and the result-
ing solid was crystallized from toluene-MeOH to give 6 as
greenish brown crystals (125 mg, 70%). IR (KBr): ν(CN) 2058
cm-1
.
1H NMR (C6D6, 400 MHz, methylene protons in the
cyclohexenyl groups are omitted): δ 6.34 (s, 1H, η1:η2-µ-
C{C(CdCHa(CH2)3CH2)dCHbSPri}dCH{CdCHc(CH2)3CH2}),
6.30, 5.56 (br s, 1H each, Ha and Hc), 3.33, 2.88 (sep, 1H each,
J ) 6.7 Hz, SCHMe2), 1.95, 1.52 (s, 15H each, C5Me5), 1.76,
1.54, 1.45, 1.39 (d, 3H each, J ) 6.7 Hz, SCHMe2), 1.09 (s, 9H,
But). The signal for the vinyl proton attached to the coordi-
nated carbon-carbon double bond could not be assigned, which
is presumably overlapping with the signals due to methylene
protons. Anal. Calcd for C47H73NS2Ru2: C, 61.47; H, 8.01;
N, 1.53. Found: C, 60.85; H, 8.11; N, 1.57.
Reaction of Din u clear Metallacycle 4 with CO. Through
a solution of 4 (181 mg, 0.217 mmol) in toluene (10 mL) was
bubbled CO gas for 30 min at room temperature, and the
solution was stirred at 80 °C under CO atmosphere for 6 h.
During this period the color of the solution changed from dark
brown to reddish orange. After removal of the solvent under
reduced pressure, the resulting solid was dissolved in hexane
and loaded on an activated alumina column. Elution with
benzene/hexane (1/9) gave the uncharacterizable orange oily
material (38 mg). A yellow band was successively obtained
upon elution with THF/hexane (1/2), from which Cp*Ru-
(CO)2SPri was isolated as yellow crystals (49 mg, 62%) after
removal of the solvent followed by crystallization of the residue
from hexane at -78 °C. IR (KBr): ν(CO) 2006, 1948 cm-1. 1H
NMR (C6D6, 270 MHz): δ 3.10 (sep, 1H, J ) 6.6 Hz, SCHMe2),
1.61 (d, 6H, J ) 6.6 Hz, SCHMe2), 1.54 (s, 15H, C5Me5). Anal.
Calcd for C15H22O2SRu: C, 49.03; H, 6.03. Found: C, 49.46;
H, 6.16.
Ack n ow led gm en t. This work was supported by the
Ministry of Education, Science, and Culture of J apan.
M.N. acknowledges the J SPS Research Fellowships for
Young Scientists.
Su p p or tin g In for m a tion Ava ila ble: Tables of thermal
parameters and complete bond distances and angles for 3, 4,
5‚1/2C7H8, and 6 and tables of hydrogen atom coordinates for
5‚1/2C7H8 and 6 (34 pages). Ordering information is given on
any current masthead page.
X-r a y Cr ysta llogr a p h ic Stu d ies. Crystals suitable for the
X-ray analysis were sealed in glass capillaries under Ar and
mounted on a four-circle diffractometer equipped with a
graphite monochromator. The data collection was performed
at room temperature. Intensity data were corrected for the
Lorentz-polarization effect and for absorption. Details of the
X-ray crystallography for 3, 4, 5‚1/2C7H8, and 6 are summarized
in Table 1. In all cases, structure solution and refinements
by assuming space group P1 instead of P1h were unsuccessful.
OM950690T
(20) Sakurai, T.; Kobayashi, K. Rep. Inst. Phys. Chem. Res. 1979,
55, 69.
(21) Sheldrick, G. M. SHELXS-86, Program for Crystal Structure
Determination. University of Go¨ttingen, Go¨ttingen, Germany, 1986.
(22) TEXSAN: TEXRAY Structure Analysis Package. Molecular
Structure Corp., 1985.
Nishio, Masayuki
