Ligand Sphere Conversions in Terminal Carbide Complexes

Article abstract of DOI:10.1021/acs.organomet.5b00803

Metathesis is introduced as a preparative route to terminal carbide complexes. The chloride ligands of the terminal carbide complex [RuC(Cl)₂(PCy₃)₂] (RuC) can be exchanged, paving the way for a systematic variation of the ligand sphere. A series of substituted complexes, including the first example of a cationic terminal carbide complex, [RuC(Cl)(CH₃CN)(PCy₃)₂]⁺, is described and characterized by NMR, MS, X-ray crystallography, and computational studies. The experimentally observed irregular variation of the carbide ¹³C chemical shift is shown to be accurately reproduced by DFT, which also demonstrates that details of the coordination geometry affect the carbide chemical shift equally as much as variations in the nature of the auxiliary ligands. Furthermore, the kinetics of formation of the sqaure pyramidal dicyano complex, trans-[RuC(CN)₂(PCy₃)₂], from RuC has been examined and the reaction found to be quite sluggish and of first order in both RuC and cyanide with a rate constant of k = 0.0104(6) M^-1 s^-1. Further reaction with cyanide leads to loss of the carbide ligand and formation of trans-[Ru(CN)₄(PCy₃)₂]^2-, which was isolated and structurally characterized as its PPh₄⁺ salt.

Full text of DOI:10.1021/acs.organomet.5b00803

Article
pubs.acs.org/Organometallics
Ligand Sphere Conversions in Terminal Carbide Complexes
Thorbjørn J. Morsing, Anders Reinholdt, Stephan P. A. Sauer, and Jesper Bendix*
Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 København Ø, Denmark
*
S Supporting Information
ABSTRACT: Metathesis is introduced as a preparative route to terminal carbide
complexes. The chloride ligands of the terminal carbide complex [RuC(Cl) (PCy ) ]
2
3 2
(
RuC) can be exchanged, paving the way for a systematic variation of the ligand sphere.
A series of substituted complexes, including the first example of a cationic terminal
carbide complex, [RuC(Cl)(CH CN)(PCy ) ] , is described and characterized by
+
3
3 2
NMR, MS, X-ray crystallography, and computational studies. The experimentally
1
3
observed irregular variation of the carbide C chemical shift is shown to be accurately
reproduced by DFT, which also demonstrates that details of the coordination geometry
affect the carbide chemical shift equally as much as variations in the nature of the
auxiliary ligands. Furthermore, the kinetics of formation of the sqaure pyramidal dicyano
complex, trans-[RuC(CN) (PCy ) ], from RuC has been examined and the reaction
2
3 2
found to be quite sluggish and of first order in both RuC and cyanide with a rate constant of k = 0.0104(6) m s−1. Further
−
1
2−
reaction with cyanide leads to loss of the carbide ligand and formation of trans-[Ru(CN) (PCy ) ] , which was isolated and
4
3 2
structurally characterized as its PPh4+ salt.
INTRODUCTION
the peripheral ligand sphere of terminal carbide complexes have
barely been investigated. The only experimental report of such
reactivity is Johnson’s description that [OsC(Cl) (PCy ) ]
■
The chemistry of molecular carbides is currently in rapid
2
3 2
development. In fuel synthesis by the Fischer−Tropsch
1
exchanges its chloride ligands for iodide upon reaction with
process, carbide ligands on catalyst surfaces are possibly key
28
2
Me SiI. However, computational studies suggest variation of
3
intermediates, entering C−C bond forming steps. Addition-
ally, the remarkable report of a central interstitial carbide ligand
in the FeMo-cofactor of nitrogenase suggests that carbide
ligands may tune catalytic properties. Metal complexes with
terminal carbide ligands (groups 6 and 8)
compared with complexes with other monatomic terminal
the ligand sphere to be a powerful entry to manipulation of the
stability and electronic properties of terminal carbide moieties.
Consequently, we have investigated the feasibility of ligand
3
4
−10
substitution in the terminal carbide [RuC(Cl)
(PCy ) ] (RuC).
2 3 2
are relatively rare
This, remarkably stable carbide complex was first synthesized
6
7
by Heppert and further investigated by Grubbs and
Johnson.
ligands such as fluoride, oxide, or nitride. In contrast to the
9,29
11
12,13
Here, it will be demonstrated, that despite the
situation for oxide and nitride
complexes, no preparative
robust nature of RuC, ligand substitutions which preserve the
terminal carbide ligand are feasible and provide a useful
approach to systematic modifications of the environment of the
terminal carbide ligand.
routes to carbide complexes involving atom-transfer reactions
have been found. Thus, only two strategies for forming terminal
carbide complexes exist. Cleaving of carbon-derived ligands
provides by far the most explored route to terminal carbide
4
−10
complexes.
The second strategy of auxiliary ligand sphere
RESULTS AND DISCUSSION
■
modification provides a simple, though virtually unexplored,
1
0
Reaction of a chloroform solution of RuC with a suitable
approach.
cyanide salt, e.g., (Ph P)CN, results in ligand exchange and the
As might be anticipated, most reported chemistry of terminal
carbide systems engages the carbide ligand of the MC: unit.
These reactions cover functionalization with nonmetals to
incorporate the carbon atom into larger organometallic
4
formation of [RuC(CN) (PCy ) ], (RuC-(CN) ) (see Scheme
2
3 2
2
1
). The exchange is relatively slow (vide infra), and with a 2−3
fold excess of cyanide, the reaction is complete after 30 min as
13
4
,8−10,14,15
shown by C NMR, during which time the color changes from
yellow to almost colorless. The complex decomposes relatively
fast in the chloroform solution mixture, hampering its isolation.
However, when the reaction is performed in dichloromethane,
the solution is comparatively stable, and upon concentration, it
precipitates an off-white powder that can be recrystallized from
boiling acetonitrile. The reaction between RuC and cyanide to
fragments
and bridge formation with transition
metal fragments to afford heterometallic carbide-bridged
7
,16
complexes.
Similarly, carbide ligands coordinated to main
group metals, MC−M′, are prone to react like their terminal
congeners thus participating in relay-like reactions where
transition metal or other main group fragments replace the
17
main group metal fragments at the carbide ligands. Contrary
18
13,19
to complexes with terminal nitride ligands [VN], [CrN],
2
0
21
22
23
24
25
[
[
MoN], [WN], [MnN], [TcN], [ReN], [RuN], and
Received: September 18, 2015
2
6
27
OsN], or bridging carbide ligands, substitution reactions in
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.organomet.5b00803
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Scheme 1. Synthetic Routes to RuC-(CN) and Mono-
Substituted Species, RuC-X
Cl angle of 102.8° for RuC. A similar trend is observed in RuC-
MeCN where the C−Ru−Cl angle is 103.20(7)°, and the C−
Ru−N angle is 97.41(8)°. Cyanide and acetonitrile are π-
backbonding ligands, and optimal overlap for backbonding
requires the C−Ru−L angle to be close to 90°, which might
explain the smaller angles for these ligands compared to that of
chloride.
2
13
C NMR is convenient for monitoring reactions with RuC
due to the ease of 13C-labeling of the carbide ligand using C-
labeled vinyl acetate. The characteristic high chemical shifts for
the terminal carbide (>450 ppm) make it easy to identify
changes in the environment around the carbide. Table 1 lists
chemical shifts of RuC as well as of the new terminal carbide
complexes synthesized in this study.
13
form RuC-(CN) relies on the ready association of cyanide
2
with ruthenium. In contrast to this, fluoride, bromide, iodide,
azide, cyanate, and thiocyanate fail to substitute the chloride
ligands directly. However, chloride abstraction, using Tl in
+
acetonitrile, affords the monosubstituted cationic [RuC(Cl)-
Table 1. [RuC(X)(Y)(PR ) ] Carbide 13C Resonances in
+
3
2
(
MeCN)(PCy ) ] , RuC-MeCN. Mass spectra of RuC-MeCN
3
2
Chloroform (R = Cy) and Calculated for Model Systems (R
Me)
reveal cations with m/z = 750.38 and 709.35 corresponding to
RuC-MeCN and its acetonitrile-deprived derivative, suggesting
weak coordination of MeCN. The conversions capitalize on this
aspect, as the cationic terminal carbide complex readily traps
halides and pseudohalides (X = F , Br , I , CN , NCO , and
NCS ) to form [RuC(Cl)(X)(PCy ) ] (RuC-X), thus enabling
=
experimental shift
R = Cy/ppm
calculated shift
R = Me/ppm
compound
[RuC(PR ) Cl ], RuC
−
−
−
−
−
471.7
464.7
470
467
3
2
2
−
3
2
[RuC(PR ) (CN) ],
3 2 2
RuC-(CN)2
the isolation of systematically modified terminal carbide
complexes.
X-ray crystal structures were obtained for the compounds
[
[
[
[
RuC(PR ) ClF], RuC-F
473.4
471.4
469.7
474.9
474
466
463
476
3
2
RuC(PR ) ClBr], RuC-Br
3 2
RuC(PR ) ClI], RuC-I
RuC-(CN) , RuC-MeCN, RuC-NCO, RuC-CN, and RuC-Br.
3 2
2
RuC(PR ) Cl(CN)],
Thermal ellipsoid plots of the first two are given in Figure 1 and
3
2
RuC-CN
[
[
[
[
RuC(PR ) Cl(NCO)],
473.5/474.7
473.5/474.7
477.5
480
485
484
493
3
2
RuC-NCO
RuC(PR ) Cl(OCN)],
3
2
RuC-NCO
RuC(PR ) Cl(NCS)],
3
2
RuC-NCS
+
RuC(PR ) Cl(NCCH )] ,
485.7
3
2
3
RuC-MeCN
In the RuC-X series where X = F, Cl, Br, and I, the carbide
resonances change as would be expected based on the
electronegativity of X, namely, from relatively deshielded
carbide resonances in RuC-F to relatively shielded carbide
resonances in RuC-I. An irregular trend is observed in the
cyanide-substituted species. Exchanging one chloride in RuC
(
471.7 ppm) for cyanide to give RuC−CN yields a more
deshielded carbide (474.9 ppm), but exchanging both chlorides
for cyanides to give RuC-(CN) yields a less deshielded carbide
2
(
464.7 ppm). This clearly demonstrates the difficulty in
simplistic interpretation of carbide resonance positions in
terms of molecular composition.
To elucidate the variations in δ , a DFT study was performed
C
to dissect the variation in the chemical shifts of the carbide
ligands. A DFT approach with geometry optimized structure
models with PMe emulating PCy , the PBE0 functional, and
3
3
Figure 1. Thermal ellipsoid plots of RuC-(CN)2 (top) and the
complex cation of RuC-MeCN (bottom) shown at 50% probability
and with hydrogen atoms omitted.
ZORA treatment of relativistic effects (cf. SI for more details of
the computations) yielded calculated shifts in remarkable
agreement with experiment, both qualitatively and quantita-
tively (cf. Table 1). Numerical values are correct within 9 ppm,
often better, and trends within substitution series are
reproduced, including the upfield shift of the carbide
resonances in RuC-X when X changes to heavier halides, as
well as the aforementioned puzzling trend in the RuC/RuC−
the remaining, structurally similar examples are shown in the
Figure S1. The ruthenium-carbide distances vary only a little in
the complexes falling in the range 1.636(3)−1.645(2) Å. For
RuC-(CN) , Ru-CN distances are 2.071(3) and 2.076(3) Å,
2
slightly longer than the average Ru-CN distance (2.01(5) Å)
CN/RuC-(CN) series. The origin of this irregular variation
2
for structures in the CSD. The C−Ru−CN angles are
was investigated further. The ruthenium−carbide distances are
nearly constant for the systems (vide supra), and thus, the most
9
9.20(13) and 99.36(15)°, which is smaller than the C−Ru−
B
DOI: 10.1021/acs.organomet.5b00803
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
obvious geometrical difference lies in the C−Ru−L angles. The
angular variation is reproduced in the geometry optimized
model systems, and importantly, for the RuC−CN model, the
C−Ru−Cl angle is larger than the C−Ru−CN angle, thus
mirroring the crystal structures. To investigate the angular
calculated magnitudes of the coupling constants in combination
with the experimentally observed line widths.
The conversion of RuC with cyanide to afford RuC-(CN) is
2
relatively slow and can be monitored by NMR (cf. Figure 2).
Steady-state kinetics experiments with a > 20-fold excess of
cyanide were performed for a range of cyanide concentrations,
and a second order rate constant for the formation of RuC-
dependence of the chemical shifts, we evaluated δ for the RuC
C
model [RuC(Cl) (PMe ) ] with the bond angles for RuC-
2
3 2
−
1
(
CN) and vice versa. These calculations suggested that two
(CN) in chloroform was determined to be k = 0.0104(6) M
s
2
2
2
−1
competing effects produce the observed chemical shifts. For the
chloride/cyanide ligand systems, the effect of the different
geometries and the nature of the ligand are of the same
magnitude (both on the order of 25 ppm) but with opposite
signs, thereby almost canceling out, and the observed trend is
therefore the result of this tug of war (see SI for details). Table
(see SI for details). The reaction is slow compared with
substitution reactions involving the association of cyanide with
3
0
phthalocyanine or porphyrin complexes of ruthenium (k =
0.052−41(1) m s ).
2
−1 −1
The reaction is first order in cyanide, suggesting initial
conversion of RuC to the apparently more reactive
monosubstituted RuC-CN, which reacts rapidly to form
2
contains experimental and calculated coupling constants, and
RuC-(CN) . This enhanced reactivity is underlined by the
absence of H-resonances from RuC-CN in the reaction
2
1
Table 2. Experimental and Calculated NMR Parameters for
RuC and RuC-(CN) and Their Model Systems
mixture. Moreover, mass spectra of RuC-CN in MeCN yield
intense signals with m/z = 741.41 and 700.38, corresponding to
2
δC
carbide)
(ppm)
δC
+
+
(
(cyanide) 2JC−P 2JC‑CN 2JP‑CN
[RuC(CN)(MeCN)(PCy ) ] and [RuC(CN)(PCy ) ] ,
3 2 3 2
compound
(ppm)
(Hz)
(Hz)
(Hz)
which suggests that the cyanide in RuC-CN labilizes the
remaining chloride ligand. As mentioned, RuC-(CN)2 is
unstable in the cyanide-containing chloroform solutions and
decomposes over the course of 5−8 h depending on the
cyanide concentration. A broad 13C NMR signal at 121.9 ppm
in chloroform suggests that excess cyanide reacts with the
[
[
[
[
RuC(Cl) (PCy ) ],
471.7
4.16
2
3 2
RuC
RuC(Cl) (PMe ) ]
471
−2.0
2
3 2
(calc.)
RuC(CN) (PCy ) ],
464.7
467
136.7
145
not
res.
not
res.
13.7
17.4
2
3 2
RuC-(CN)2
solvent to form the very strong acid CH(CN) (pK = −5.0,
RuC(CN) (PMe ) ]
0.47
−0.64
3
a
2
3 2
31
(calc.)
anion δ ,
= 121.4). After 5 days, excess cyanide has
C
CN
vanished, though a 20-fold excess was used. RuC is known to
8
,10,15
decompose in acidic solutions,
and RuC-(CN) parallels
2
in contrast to the well-resolved coupling to phosphorus in
this instability. However, the decomposition product isolated
here is not a carbene complex; rather, a relatively clean
conversion into a ruthenium(II) complex trans-[Ru-
2
parent RuC (virtual t, J
= 4.16 Hz), the carbide resonance
C−P
1
3
in RuC-(CN) appears as a singlet, also with CN in the ligand
2
2
−
13
sphere. However, the cyanide signal at 136.7 ppm is a triplet
(CN) (PCy ) ] takes place. The C NMR signal from the
4 3 2
2
2
(
JC−P = 13.7 Hz); these findings are also corroborated by the
cyanide ligand is a triplet (160.2 ppm, J
= 13.1 Hz), and in
C−P
1
Figure 2. H NMR spectra in the δ = 0.9−2.6 ppm region showing the reaction between RuC and cyanide in chloroform. Blue arrows indicate the
first reaction where RuC is converted into RuC-(CN) , and red arrows indicate the second reaction where RuC-(CN) decomposes to trans-
2
2
2
−
[
Ru(CN) (PCy ) ] . The top panels show fitted concentration curves for the three species.
4 3 2
C
DOI: 10.1021/acs.organomet.5b00803
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
3
1
2
P NMR, a corresponding quintet (33.4 ppm, J
= 13.1 Hz)
yellow crystals of RuC-MeCN were separated from the mother liquor
by decanting, washed with 15 mL of diethyl ether, and air-dried. Yield:
C−P
1
3
−
is observed with CN . The complex was isolated as the
tetraphenylphosphonium salt and characterized by X-ray
crystallography (cf. SI).
4
3.8 mg, 48.7 μmol, 34.5% based on RuC. Crystals suitable for X-ray
1
crystallography were grown by this procedure. H NMR, 500 MHz,
CD Cl , δ: 2.80 (s, 3H), 2.52−2.39 (m, 6H), 2.20−2.13 (m, 6H),
2
2
2
.13−2.07 (m, 6H), 1.97−1.87 (m, 12H), 1.82−1.75 (m, 6H), 1.72−
CONCLUSIONS
13
■
1.60 (m, 6H), 1.53−1.41 (m, 6H), 1.39−1.24 (m, 18H). C NMR,
126 MHz, CDCl , δ: 485.70, 137.87, 32.78 (virtual t, J
30.46, 29.89, 28.03 (virtual t, JC−P = 5.1 Hz), 27.83 (t, J = 5.5 Hz),
1
It is possible to vary the auxiliary ligands of the ruthenium
carbide systematically by metathesis reactions, and in some
ways, this is surprising in view of the sensitivity of synthetic
= 10.2 Hz),
C−P
3
1
19
2
6.47, 5.24. 31P NMR, 202 MHz, CD Cl , δ: 43.37. F NMR, 470
2 2
+
7
MHz, CD Cl , δ: − 78.93. ESI MS, CH CN, m/z, f/c: [RuC(Cl)-
2
2
3
routes to RuC toward the choice of phosphine ligands. The
+
+
(
MeCN)(PCy ) ] : 750.38/750.36, [RuC(Cl)(PCy ) ] : 709.35/
3
2
3
2
chloride ligands are evidently not as critical for the stability of
the RuC moiety as are the phosphine ligands, and even the
cationic complex RuC-MeCN is quite stable. This particular
complex with its labile acetonitrile ligand represents a
convenient gateway to much more elaborately decorated
terminal carbide systems for further studies.
In conclusion, we have demonstrated a facile and general
route to a family of terminal ruthenium carbide complexes with
varying auxiliary ligands. We have also demonstrated a
computational approach, which accurately predicts the chemical
shifts of such carbide species and elucidates the influence of the
coordination geometry and nature of the auxiliary ligands on
the chemical shift of the terminal carbide ligand.
7
09.34. Anal. Calcd for C H ClF NO P RuS: C 53.41%, H 7.73%,
40 69 3 3 2
N 1.56%; found, C 53.42%, H 7.88%, N 1.78%.
Synthesis of [RuC(Cl)(CN)(PCy ) ] (RuC-CN). KCN (17.8 mg,
73 μmol) and RuC-MeCN (15.0 mg, 16.7 μmol) were placed in 1
3
2
2
mL of acetonitrile and stirred for 24 h whereupon RuC-CN
precipitated. The suspension was passed through a plug of silica
(diameter 0.5 cm, length 2 cm), and the residue was washed with
acetonitrile (5 × 1 mL) and extracted with dichloromethane (5 × 1
mL). The dichloromethane was evaporated to afford RuC-CN as a
white powder. Yield: 9.9 mg, 13.5 μmol, 80.7% based on RuC-MeCN.
Crystals suitable for X-ray crystallography were grown by concentrat-
1
ing an acetonitrile solution of RuC-CN. H NMR, 500 MHz, CDCl ,
3
δ: 2.70−2.60 (m, 6H), 2.28−2.20 (m, 6H), 2.14−2.06 (m, 6H), 1.91−
1
.81 (m, 12H), 1.78−1.70 (m, 6H), 1.64−1.46 (m, 12H), 1.38−1.20
2
(
m, 18H). 13C NMR, 126 MHz, CDCl , δ: 474.91, 132.69 (t, J
=
C−P
3
1
EXPERIMENTAL SECTION
13.7 Hz), 33.16 (virtual t, J
= 10.5 Hz), 30.56, 29.83, 27.99 (virtual
= 5.4 Hz), 26.70. P NMR, 202 MHz, CDCl , δ: 44.78 (d, J =
■
9
C−P
1
31
t, J
Syntheses. Unless otherwise stated, no attempts were made to
exclude air in the syntheses. Chloroform (Sigma-Aldrich, HPLC, ≥
C−P
3
+
+
1
3.8 Hz). ESI MS, CH CN, m/z, f/c: [RuC(MeCN)(CN)(PCy ) ] :
3
3
2
+
9.8%), chloroform-d (Sigma-Aldrich, 99.8% D), dichloromethane
Sigma-Aldrich, HPLC, ≥ 99.8%), dichloromethane-d2 (Sigma-
741.41/741.40, [RuC(CN)(PCy
) ] : 700.38/700.37. Anal. Calcd for
3 2
C H ClNP Ru: C 62.06%, H 9.05%, N 1.90%; found, C 61.98%, H
(
38 66
2
9
.38%, N 1.83%.
Synthesis of [RuC(Cl)(F)(PCy
Aldrich, 99.9% D), benzene-d (Sigma-Aldrich, 99.6% D), acetonitrile
(
tetraethylammonium fluoride hydrate (Sigma-Aldrich, 98%), and
Silica Gel 60 Å (ROCC) were purchased from commercial suppliers
and used as received. [Ru(C)Cl (PCy ) ] (RuC) and TlOTf were
6
Riedel-de Hae
̈
n, > 99.9%), diethyl ether (VWR Chemicals),
)
3
2
] (RuC-F). In a plastic test tube,
N)F·H O (7.2 mg, 43 μmol,
an acetonitrile solution (0.5 mL) of (Et
4
2
2.8 equiv) was added to an acetonitrile solution (1 mL) of RuC-
MeCN (13.7 mg, 15.2 μmol). Within 10 min, yellow crystals of RuC-F
were deposited on the walls of the test tube. The mother liquor was
decanted off, and the crystals were washed with acetonitrile (3 × 1
2
3 2
9
,32
13
synthesized according to published procedures;
Ru C was
obtained with 13CH2 CHOAc (Sigma-Aldrich, 99% C). (Ph P)CN
13
13
4
was prepared by aqueous metathesis of sodium cyanide and
tetraphenylphosphonium chloride and recrystallized from water.
Synthesis of [RuC(CN) (PCy ) ] (RuC-(CN) ). RuC (35 mg (47
μmol)) and 100 mg (274 μmol) of (Ph P)CN were dissolved in 4 mL
of dichloromethane and left for 3 h. In this time, the pale yellow
solution turned almost colorless. The solution was evaporated to
dryness (with N ) and the crystalline precipitate thoroughly washed 3
times with methanol to remove excess (Ph P)CN and (Ph P)Cl
formed in the reaction. The crude product was dissolved in 25 mL of
boiling acetonitrile and left to evaporate to dryness yielding 16.3 mg of
RuC-(CN) , 48% based on RuC. H NMR, 500 MHz, CD Cl , δ:
mL) and dried in vacuo. Yield: 3.9 mg, 5.4 μmol, 35.2% based on RuC.
1
H NMR, 500 MHz, C D , δ: 2.54−2.45 (m, 6H), 2.42−2.35 (m, 6H),
6 6
2.35−2.27 (m, 6H), 1.92−1.78 (m, 12H), 1.78−1.70 (m, 12H), 1.62−
2
3 2
2
13
1.56 (m, 6H), 1.26−1.15 (m, 18H). C NMR, 126 MHz, C
D
6
, δ:
4
6
2
1
474.58 (d, JC−F = 24.4 Hz), 32.21 (virtual t, JC−P = 9.6 Hz), 30.08,
1
1
29.84, 28.16 (virtual t, JC−P = 5.5 Hz), 28.09 (virtual t, JC−P = 5.0
3
1
2
Hz), 26.92. P NMR, 202 MHz, C
D
6
, δ: 37.76 (d, JP−F = 12.5 Hz).
2
6
19
2
F-NMR, 282 MHz, C D , δ: − 423.39 (t, J
= 18.7 Hz). Anal.
4
4
6
6
F−P
Calcd for C H ClFP Ru·0.10 CH CN: C 61.00%, H 9.12%, N 0.19;
found, C 60.81%, H 8.94%, N 0.14%.
37 66 2 3
1
2
2
2
Synthesis of [RuC(Cl)(X)(PCy ) ] (RuC-X). The syntheses of the
3 2
2
1
(
.69−2.59 (m, 6H), 2.24−2.13 (m, 12H), 1.93−1.83 (m, 12H), 1.80−
remaining RuC-X systems were carried out essentially as described for
RuC-CN. KI and KNCS are slightly soluble in acetonitrile, and in the
dichloromethane extracts, these salts consequently appeared as cloudy
precipitates that were removed by filtration. Alternatively, the
.71 (m, 6H), 1.53−1.41 (m, 12H), 1.41−1.30 (m, 12H), 1.30−1.22
m, 6H). 13C NMR, 126 MHz, CD Cl , δ: 465.23, 136.43 (t, J
2
=
2
2
C−P
1
1
3.6 Hz), 35.08 (virtual t, J
C−P
t, J
= 11.0 Hz), 30.68, 28.28 (virtual t,
C−P
1
13
J
= 5.7 Hz), 26.99. C NMR, 126 MHz, CDCl , δ: 464.75, 136.81
approach used to obtain RuC-F was generally applicable to the
3
2
1
+
(
(
1
3
= 13.5 Hz), 34.68 (virtual t, J
C−P
= 11.0 Hz), 30.24, 27.78
other RuC-X systems (salts of PPh4 were used in place of (Et N)F·
C−P
C−P
4
1
31
virtual t, J
= 6.0 Hz), 26.51. P NMR, CD Cl , δ: 49.65 (t, J =
H O; (PPh )(CN), however, is not suitable for this procedure).
2
2
2 4
1
3.6 Hz). Anal. Calcd for C H N P Ru: C 64.50%, H 9.17%, N
.86%; found, C 64.14%, H 8.99%, N 3.84%.
RuC-Br: H NMR, 500 MHz, CDCl , δ 2.74−2.63 (m, 6H), 2.23−
39
66
2
2
3
2.12 (m, 12H), 1.90−1.78 (m, 12H), 1.76−1.70 (m, 6H), 1.70−1.56
1
3
Synthesis of [RuC(Cl)(MeCN)(PCy ) ]OTf (RuC-MeCN). Under
(m, 12H), 1.33−1.22 (m, 18H). C NMR, 126 MHz, CDCl , δ:
3
2
3
2
1
a N blanket, TlOTf (104.9 mg, 296.8 μmol) and RuC (105.0 mg,
1
471.38 (t, J
= 3.7 Hz), 32.39 (virtual t, J
= 10.1 Hz), 30.32,
2
C−P
C−P
1
1
41.0 μmol) were suspended in a mixture of 1 mL of chloroform and 1
30.26, 28.17 (virtual t, J
= 4.9 Hz), 28.15 (virtual t, J
= 5.1
C−P
C−P
mL of acetonitrile and heated to reflux temperature for 18 h. During
this time, the solution changed color to dark green, and a white
precipitate of TlCl formed. The solution was evaporated to dryness,
and the residue extracted with dichloromethane (2 mL) and passed
through a plug of silica (diameter 0.5 cm, length 4 cm) to absorb the
dark green byproduct. The extract was evaporated to dryness, and the
residue was dissolved in 2 mL of acetonitrile. After dilution with 50
mL of diethyl ether, the solution was left at 5 °C for 3 days. Pale
Hz), 26.85. 31P NMR, 202 MHz, CDCl , δ: 37.89. Anal. Calcd for
3
C H BrClP Ru: C 56.30%, H 8.43%; found, C 56.65%, H 8.60%.
37
66
2
1
RuC-I: H NMR, 500 MHz, CDCl , δ 2.89−2.74 (m, 6H), 2.27−
3
2.10 (m, 12H), 1.93−1.77 (m, 12H), 1.77−1.60 (m, 12H), 1.58−1.47
1
3
(m, 6H), 1.34−1.20 (m, 18H). C NMR, 126 MHz, CDCl , δ: 469.74
3
2
1
(t, J
= 3.6 Hz), 33.44 (virtual t, J
= 5.2 Hz), 28.14 (virtual t, J
26.85. P NMR, 202 MHz, CDCl , δ: 38.47. Anal. Calcd for
= 10.0 Hz), 30.92, 30.50,
C−P
C−P
1
1
28.18 (virtual t, J
= 4.7 Hz),
C−P
C−P
3
1
3
D
DOI: 10.1021/acs.organomet.5b00803
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
C H ClIP Ru·3/4 CH CN: C 53.33%, H 7.93%, N 1.21%; found, C
(6) Carlson, R. G.; Gile, M. A.; Heppert, J. A.; Mason, M. H.; Powell,
D. R.; Velde, D. V.; Vilain, J. M. J. Am. Chem. Soc. 2002, 124, 1580−
1581.
3
7
66
2
3
5
3.76%, H 8.00%, N 1.09%.
1
RuC-NCO: H NMR, 500 MHz, CDCl , δ 2.49−2.37 (m, 6H),
3
2
1
4
2
.23−2.08 (m, 12H), 1.93−1.81 (m, 12H), 1.79−1.69 (m, 6H), 1.68−
.49 (m, 12H), 1.37−1.21 (m, 18H). C NMR, 126 MHz, CDCl , δ:
(7) Hejl, A.; Trnka, T. M.; Day, M. W.; Grubbs, R. H. Chem.
1
3
3
Commun. 2002, 2524−2525.
2
1
73.51 (t, J
= 3.8 Hz), 134.41, 32.24 (virtual t, J
= 9.8 Hz),
= 4.9
C−P
(8) Romero, P. E.; Piers, W. E.; McDonald, R. Angew. Chem., Int. Ed.
2004, 43, 6161−6165.
C−P
C−P
1
1
9.93, 28.08 (virtual t, J
Hz), 26.74. P NMR, 202 MHz, CDCl , δ: 41.23. Anal. Calcd for
= 5.1 Hz), 28.04 (virtual t, J
C−P
31
3
(9) Caskey, S. R.; Stewart, M. H.; Kivela, J. E.; Sootsman, J. R.;
Johnson, M. J. A.; Kampf, J. W. J. Am. Chem. Soc. 2005, 127, 16750−
C H ClNOP Ru: C 60.74%, H 8.85%, N 1.86%; found, C 60.78%, H
38
66
2
9
.06, N 2.00%.1
1
6751.
RuC-NCS: H NMR, 500 MHz, CDCl , δ: 2.51−2.39 (m, 6H),
3
(10) Stewart, M. H.; Johnson, M. J. A.; Kampf, J. W. Organometallics
2
.23−2.15 (m, 6H), 2.15−2.06 (m, 6H), 1.92−1.83 (m, 12H), 1.80−
.71 (m, 6H), 1.69−1.58 (m, 6H), 1.58−1.47 (m, 6H), 1.41−1.22 (m,
2
(
(
007, 26, 5102−5110.
1
11) Holm, R. H. Chem. Rev. 1987, 87, 1401−1449.
1
8H). 13C NMR, 126 MHz, CDCl , δ: 477.50, 149.43, 32.44 (virtual t,
3
12) Bottomley, L. A.; Neely, F. L. J. Am. Chem. Soc. 1989, 111,
1
1
JC−P = 10.1 Hz), 30.09, 29.81, 28.15 (virtual t, J
5.4 Hz), 28.01
= 5.2 Hz), 26.71. P NMR, 202 MHz, CDCl , δ:
C−P
5
955−5957. Woo, L. K.; Goll, J. G.; Czapla, D. J.; Hays, J. A. J. Am.
1
31
(
virtual t, J
C
−
P
3
Chem. Soc. 1991, 113, 8478−8484. Neely, F. L.; Bottomley, L. A. Inorg.
Chim. Acta 1992, 192, 147−149. Bottomley, L. A.; Neely, F. L. Inorg.
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Inorg. Chem. 1997, 36, 270−271.
4
1
2.73. Anal. Calcd for C H ClNP RuS: C 59.47%, H 8.67%, N
.83%; found, C 58.93%, H 8.87%, N 1.76%.
38 66 2
ASSOCIATED CONTENT
(13) Bendix, J. J. Am. Chem. Soc. 2003, 125, 13348−13349. Birk, T.;
Bendix, J. Inorg. Chem. 2003, 42, 7608−7615. Hedegaard, E. D.;
Schau-Magnussen, M.; Bendix, J. Inorg. Chem. Commun. 2011, 14,
■
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.5b00803.
7
(
19−721.
14) Greco, J. B.; Peters, J. C.; Baker, T. A.; Davis, W. M.; Cummins,
C. C.; Wu, G. J. Am. Chem. Soc. 2001, 123, 5003−5013. Caskey, S. R.;
Stewart, M. H.; Johnson, M. J. A.; Kampf, J. W. Angew. Chem., Int. Ed.
Description of physical methods; molecular structure
2
006, 45, 7422−7424. Cummins, C. C. Angew. Chem., Int. Ed. 2006,
plots and crystallographic information for RuC-Br, RuC-
2
−
45, 862−870. Mutoh, Y.; Kozono, N.; Araki, M.; Tsuchida, N.;
Takano, K.; Ishii, Y. Organometallics 2010, 29, 519−522.
(
CN, RuC-NCO, and [Ru(PCy ) (CN) ] ; details of
3
2
4
computations; and additional kinetic data and selected
NMR spectra (PDF)
15) Macnaughtan, M. L.; Johnson, M. J. A.; Kampf, J. W. J. Am.
Chem. Soc. 2007, 129, 7708−7709.
(16) Reinholdt, A.; Vibenholt, J. E.; Morsing, T. J.; Schau-
Magnussen, M.; Reeler, N. E. A.; Bendix, J. Chem. Sci. 2015, 6,
Crystallographic data for RuC-Br, RuC-CN, RuC-NCO,
2−
and [Ru(PCy ) (CN) ] (ZIP)
3
2
4
5
(
815−5823.
17) Etienne, M.; White, P. S.; Templeton, J. L. J. Am. Chem. Soc.
AUTHOR INFORMATION
■
*
1991, 113, 2324−2325. Colebatch, A. L.; Cordiner, R. L.; Hill, A. F.;
Nguyen, K. T. H. D.; Shang, R.; Willis, A. C. Organometallics 2009, 28,
Corresponding Author
E-mail: bendix@kiku.dk.
4
394−4399. Cordiner, R. L.; Hill, A. F.; Shang, R.; Willis, A. C.
Organometallics 2011, 30, 139−144. Hill, A. F.; Sharma, M.; Willis, A.
C. Organometallics 2012, 31, 2538−2542. Borren, E. S.; Hill, A. F.;
Shang, R.; Sharma, M.; Willis, A. C. J. Am. Chem. Soc. 2013, 135,
Notes
The authors declare no competing financial interest.
4
(
942−4945.
18) Johnson, C. E.; Kysor, E. A.; Findlater, M.; Jasinski, J. P.; Metell,
A. S.; Queen, J. W.; Abernethy, C. D. Dalton Trans. 2010, 39, 3482−
488.
19) Bendix, J.; Birk, T.; Weyhermuller, T. Dalton Trans. 2005,
737−2741. Brock-Nannestad, T.; Hammershøi, A.; Schau-
Magnussen, M.; Vibenholt, J.; Bendix, J. Inorg. Chem. Commun.
ACKNOWLEDGMENTS
■
The Danish Research Council for Independent Research is
acknowledged for funding (Grant 12-125226).
3
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DOI: 10.1021/acs.organomet.5b00803
Organometallics XXXX, XXX, XXX−XXX