Li et al.
173
calcd. for C42H46N2P2BClF4Ru: C 58.08, H 5.46, N 3.33;
found: C 58.40, H 5.33, N 3.24.
NOE measurements
1
The H NOESY NMR experiment was acquired by the
standard three-pulse sequence (43). Each transient (direct di-
mension) was acquired using 2K points; the number of tran-
sients (indirect dimension) was 1K, and the number of scans
was set at 16. A relaxation delay of 2 s and a mixing time of
0.5 s were used. The average interionic distances were ob-
tained taking into account that the volumes of the NOE cross
peaks are proportional to (nInS/nI+nS), where nI and nS are
the number of equivalent I and S nuclei, respectively (30).
The reaction of RuHCl{tmeP2(NH)2} with HBF4
A
mixture of two isomers (see Discussion) of
RuHCl{tmeP2(NH)2} (10 mg, 0.012 mmol) was dissolved in
CD2Cl2 (1 mL) in an NMR tube under Ar. HBF4 (54 wt% in
1
Et2O, 10 mg, 0.06 mmol) was added to the solution. H
NMR δ: 7.6–6.8 (m, 28H, Ph), 4.8 (m, CH2), 4.6 (m, CH2),
4.4 (m, NH), 3.9 (m, NH), 1.8–1.2 (m, 12H, CH3), –10.9
(brs, 2H, RuH2); T1 = 19 ms at 400 MHz NMR spectrometer
PGSE measurements
2
at 293 K. 31P NMR δ: 41.0 (d, JPP = 25 Hz, 40%, isomer
1H PGSE NMR measurements were performed using the
standard stimulated echo pulse sequence (32) on a Bruker
AVANCE DRX 400 spectrometer equipped with a GREAT
1/10 gradient unit and a QNP probe with a Z-gradient coil,
at 299 K without spinning. The shape of the gradients was
rectangular, their duration was 5 ms, and their strength (G)
was varied during the experiments. All the spectra were ac-
quired using 32K points, a spectral width of 5000 Hz, and
processed with a line broadening of 1.0 Hz. The semilo-
garithmic plots of ln(I/I0) vs. G2 (where I and I0 are the in-
tensities of the observed spin echo in the presence or in the
absence of the field gradient, respectively) (34, 35) were fit-
ted using a standard linear regression algorithm; the R factor
was always higher than 0.99. rH, VH, and N values were de-
rived from experimentally determined Dt data as described
in ref. 31.
B), 30.5 (d, 37%, isomer B), 37.0 (s, 23%, isomer A). Crys-
tals of [Ru(H2)Cl{tmeP2(NH)2}]BF4 were prepared by slow
diffusion of diethyl ether into the NMR solution of the com-
plex in CD2Cl2 under Ar.
The reaction of [Ru(H2)Cl(PPh3)2(dach)]BF4 with D2
[Ru(H2)Cl(PPh3)2(dach)]BF4 (10 mg, 0.011 mmol) was
dissolved in C6D6 (1 mL) in a 5 mm NMR tube under Ar.
The solution was frozen in liquid N2 and degassed – refilled
with D2 gas for three cycles. The NMR tube was sealed with
a flame under D2 and warmed up to room temperature. An
1H NMR spectrum was collected immediately and after
15 h. A 1:1:1 triplet of 1:2:1 triplets at –10.74 ppm (1JHD
28.5 Hz, JHP = 8.7 Hz) was observed over time due to
=
2
Ru(HD).
X-ray diffraction structure determination of [Ru(H2)Cl-
(PPh3)2(dach)]BF4 and [Ru(H2)Cl{tmeP2(NH)2}]BF4
Crystals suitable for X-ray diffraction were obtained by
vapor diffusion. Data were collected on a Nonius Kappa-
CCD diffractometer using monochromated Mo Kα radiation
and were measured using a combination of φ scans and ω
scans with κ offsets, to fill the Ewald sphere. The data were
processed using the Denzo-SMN package (44). For the sec-
ond structure (the tmeP2(NH)2 complex), absorption correc-
tions were carried out using SORTAV (45). The structures
were solved and refined using SHELXTL V6.1 (46) for full-
matrix least-squares refinements that are based on F2. The H
atoms of the dihydrogen were refined independently with
isotropic displacement parameters, but in the first structure
these parameters were tied to the Ueq values of the Ru at-
oms. All other H atoms were included in calculated posi-
tions and allowed to refine in riding-motion approximation
with Uiso tied to the carrier atom. Crystallographic data for
the compounds are given in Tables 7 and 8, and selected
bond distances and angles in Tables 9 and 10.
The reaction of [Ru(H2)Cl{tmeP2(NH)2}]BF4 with D2
The procedure used for the dach complex was followed.
No H–D coupling was observed. The hydride signal at
–10.9 ppm disappeared after 15 h.
The reaction of RuHCl{tmeP2(NH)2} with HBF4(Et2O)–D2
RuHCl{tmeP2(NH)2} (isomer A, 10 mg, 0.012 mmol) was
dissolved in CD2Cl2 (1 mL) in an NMR tube. DBF4 (1 drop,
prepared by mixing HBF4, 54 wt% in Et2O, 0.40 g,
0.025 mol and degassed D2O, 1.1 g, in a Schlenk flask) was
added to the solution. A 1:1:1 triplet of triplets was observed
1
over time due to Ru(HD). H NMR δ: –10.9 (tt, RuHD,
2
2
1JHD = 28.5 Hz, JHP = 8.4 Hz). 31P NMR δ: 40.6 (d, JPP
=
25 Hz, isomer B), 30.5 (d, isomer B).
Determination of equilibrium constants in CD2Cl2
Solutions of samples were mixed under N2 as described in
Tables 3 and 4. In general, equilibrium constants were deter-
1
mined by H and 31P{1H} NMR. Usually, signals for all of
the species in equilibrium could be located and integrated in
the 31P{1H} NMR and, in the case of hydride complexes, in
the H NMR spectra as well. The chemical shifts for the
Acknowledgment
1
pure phosphines and phosphonium salts (Table 6) were de-
termined and referenced to the P(OMe)3 standard at
141.5 ppm. In some cases, when the chemical shifts of two
species are very similar, mass-balance arguments can be
used to estimate the equilibrium concentration of the species
from their starting concentrations. Thermodynamic data for
the equilibria in CD2Cl2 are shown in Tables 3 and 4.
This work was supported by a discovery grant to RHM
from the Natural Sciences and Engineering Research Coun-
cil of Canada (NSERC) and by a grant to AM from the
Ministero dell’Istruzione, dell’Università e della Ricerca
(MUIR) (PRIN 2004-2005). We thank J. Matthey for a loan
of ruthenium salts and Dr. K. Abdur-Rashid for assistance
with some experiments.
© 2006 NRC Canada
Li, Tianshu
