5
318 Organometallics, Vol. 20, No. 25, 2001
Sanford et al.
1
to loss of pyridine under vacuum. H NMR (C
1
8
)
6
D
6
): δ 19.67 (s,
5.69 (t, 1H, Tp, J HH ) 2.4 Hz), 5.50 (t, 1H, Tp, J HH ) 1.8 Hz),
H, CHPh), 8.84 (br. s, 2H, pyridine), 8.39 (br. s, 2H, pyridine),
.07 (d, 2H, ortho CH, J HH ) 8 Hz), 7.15 (t, 1H, para CH, J HH
7 Hz), 6.83-6.04 (br. mulitiple peaks, 9H, pyridine, Mes
CH), 3.37 (br. d, 4H, CH CH ), 2.79 (br. s, 6H, Mes CH ), 2.45
), 2.04 (br. s, 6H, Mes CH ). C{ H} NMR
): δ 314.90 (m, RudCHPh), 219.10 (s, Ru-C(N) ), 152.94,
3.77 (br. d, 4H, CH
ortho CH , para CH
RudCHPh), 220.57 (s, Ru-C(N)
2 2
CH ), 2.91-0.893 (br. multiple peaks, 18H,
13 1
3
3
). C{ H} (CD
2 2
Cl ): δ 324.29 (m,
2
), 151.50, 146.08, 145.39,
2
2
3
142.07, 137.94, 136.57, 134.41, 133.18, 130.60 (br), 129.55,
127.98, 106.41, 105.19, 104.51, 53.77 (br), 21.26, 20.32 (br).
Anal. Calcd for C37H N ClBRu: C, 59.56; H, 5.67; N, 15.02.
42 8
Found: C, 59.20; H, 5.67; N, 14.72.
5 5
Kin etics of th e Rea ction of 2 w ith C D N. In a cuvette
1
3
1
(br. s, 6H, Mes CH
3
3
(C
6
D
6
2
1
1
50.84, 139.92, 138.38, 136.87, 135.99, 134.97, 131.10, 130.11,
29.88, 128.69, 123.38, 51.98, 51.37, 21.39, 20.96, 19.32. Anal.
Calcd for C33
C, 61.25; H, 5.76; N, 6.58.
Rep r esen ta tive Syn th esis of a P h osp h in e Com p lex:
H
37
N
3
Cl
2
Ru: C, 61.20; H, 5.76; N, 6.49. Found:
fitted with a rubber septum, a solution of 2 (0.88 mM) in
toluene (1.6 mL) was prepared. This solution was allowed to
thermally equilibrate in the UV-vis spectrometer at 20 °C.
(
IMesH
2
)(P P h
3
)(Cl)
2
Ru dCHP h (4). Complex 3 (150 mg, 0.21
5
Neat pyridine-d (25-100 µL) was added via microsyringe, and
mmol) and PPh
3
(76 mg, 0.28 mmol) were combined in benzene
the reaction kinetics was followed by monitoring the disap-
pearance of starting material (502 nm). For each run, the data
were collected over five half-lives and were fitted to a first-
(
10 mL) and stirred for 10 min. The solvent was removed under
vacuum, and the resulting brown residue was washed with 4
20 mL of pentane and dried in vacuo. Complex 4 was
2
×
order exponential. Typical R values for the exponential curve
3
1
1
obtained as a brownish powder (125 mg, 73% yield). P{ H}
fits were greater than 0.999.
1
NMR (C
RudCHPh), 7.70 (d, 2H, ortho CH, J HH ) 8 Hz), 7.29-6.71
multiple peaks, 20H, PPh , para CH, meta CH, and Mes CH),
.27 (s, 2H, Mes CH), 3.39 (m, 4H, CH CH ), 2.74 (s, 6H, ortho
CH ), 2.34 (s, 6H, ortho CH ), 2.23 (s, 3H, para CH ), 1.91 (s,
). C{ H} NMR (C ): δ 305.34 (m, RudCHPh),
19.57 (d, Ru-C(N) , J CP ) 92 Hz), 151.69 (d, J CP ) 4 Hz),
6
D
6
): δ 37.7 (s). H NMR (C
7
D
8
): δ 19.60 (s, 1H,
X-r a y Cr ysta l Str u ctu r e of 3. Crystal, intensity collection,
and refinement details29 are summarized in Table 1. The se-
lected crystal was mounted on a glass fiber with Paratone-N
oil and transferred to a Bruker SMART 1000 CCD area de-
tector equipped with a Crystal Logic CL24 low-temperature
device. Data were collected with ω-scans at seven æ values
(
6
3
2
2
3
3
3
1
3
1
3
2
1
1
1
J
H, para CH
3
6 6
D
3
0
2
and subsequently processed with SAINT. No absorption or
decay corrections were applied. SHELXTL30 was used to solve
(by direct methods and subsequent difference Fourier maps)
39.68, 138.35, 138.10, 138.97, 137.78, 135.89, 135.21, 135.13,
31.96, 131.65, 131.36, 130.47, 129.83, 129.59 (d, J CP ) 2 Hz),
29.15, 128.92, 128.68, 128.00, 52.11 (d, J CP ) 4 Hz), 51.44 (d,
CP ) 2 Hz), 21.67, 21.35, 21.04, 19.21. Anal. Calcd for
2
and to refine (full-matrix least-squares on F ) the structure.
There are two molecules in the asymmetric unit. All non-hy-
drogen atoms were refined anisotropically; the hydrogen atoms
were placed at calculated positions with Uiso values based on
the Ueq of the attached atom. Pertinent bond lengths and
angles for one molecule are presented in Table 2.
C
46
H
47
N
2
Cl
2
PRu: C, 66.50; H, 5.70; N, 3.37. Found: C, 66.82;
H, 5.76; N, 3.29.
t
(
IMesH
mmol) and KO Bu (3 mg, 0.027 mmol) were combined in C
0.6 mL) in an NMR tube under nitrogen. The reaction mixture
2 2
)(O Bu ) Ru dCHP h (11). Complex 3 (7.5 mg, 0.010
t
6
D
6
(
Ack n ow led gm en t. Lawrence Henling and Michael
Day are acknowledged for the X-ray crystallographic
study described herein. The authors would like to thank
the NSF for generous funding of this research. J .A.L.
thanks the NIH for a postdoctoral fellowship.
was allowed to stand for 15-20 min, during which time a color
change from green to dark red was observed, and NMR spectra
1
were recorded after 30 min. H NMR (C
RudCHPh), 7.63 (d, 2H, ortho CH, J HH ) 7 Hz), 7.2-7.1
multiple peaks, 3H, meta CH and ortho CH), 6.97 (s, 4H, Mes
CH), 3.43 (s, 4H CH CH ), 2.59 (s, 12H, ortho CH ), 2.29 (s,
H, para CH ), 1.18 (s, 18H, Bu).
Tp (IMesH )(Cl)Ru dCHP h (12). KTp (87 mg, 0.34 mmol)
and complex 3 (125 mg, 0.17 mmol) were combined in CH Cl
10 mL) and stirred for 1 h. Pentane (20 mL) was added to
6 6
D ): δ 16.56 (s, 1H,
(
2
2
3
Su p p or tin g In for m a tion Ava ila ble: Experimental data
for the synthesis of all new complexes and crystallographic
data (labeled drawings, table of atomic coordinates, complete
bond distances and angles, and anisotropic displacement
parameters) for complex 3. This material is available free of
charge via the Internet at http://pubs.acs.org.
t
6
3
2
2
2
(
precipitate the salts, and the reaction was stirred for an
additional 30 min and then cannula filtered. The resulting
bright green solution was concentrated, and the solid residue
was washed with pentane (2 × 10 mL) and methanol (2 × 10
OM010599R
(29) The Crystallographic Information File (CIF) for 3 has been
mL) and dried under vacuum to afford 12 (84 mg, 66% yield)
deposited with the Cambridge Crystallographic Data Centre as
supplementary publication no. CCDC 143577. Copies of the data can
be obtained, free of charge, on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK, (fax: +44 1223 336033 or e-mail: deposit@
ccdc.cam.ac.uk). Structure factors are available from the authors via
e-mail: xray@caltech.edu.
1
as an analytically pure green powder. H NMR (CD
2
Cl
2
): δ
1
8.73 (s, 1H, RudCHPh), 7.87 (d, 1H, Tp, J HH ) 2.4 Hz), 7.41
(d, 1H, Tp, J HH ) 2.1 Hz), 7.35-7.30 (multiple peaks, 3H, Tp
and para CH), 7.08 (d, 1H, Tp, J HH ) 1.5 Hz), 6.82 (br. s, 5H,
Mes CH, ortho CH and meta CH), 6.24 (br. s, 3H, Mes CH),
(30) Bruker 1999 SMART, SAINT, and SHELXTL; Bruker AXS
6
.16 (t, 1H, Tp, J HH ) 1.8 Hz), 5.95 (d, 1H, Tp, J HH ) 1.5 Hz),
Inc.: Madison, WI.