S
–
1
Disentangling Ligand Effects on Metathesis Catalyst Activity: Experimental and
Computational Studies of Ruthenium
–
Aminophosphine Complexes
Crystal K. Chu,
†
Tzu
-
Pin Lin,
†
Huiling Shao,
‡
Allegra L. Liberman
-
Martin,
†
Peng Liu,*
‡
and Robert H. Grubbs*
†
†
Arn
old and Mabel
Beckman Laboratori
es of Chemical Synthesis, California Institute of
Technology, Pasadena, California 91125, United States
‡
Department of Chemistry, University of Pittsburgh,
Pittsburgh,
Pennsylvania, 15260,
United States
Supporting Informat
ion
Table of Contents
I.
General Information
S
–
1
II.
Preparation of Aminophosphine Ligands
S
–
2
III.
Preparation
of Aminophosphine
-
Ligated Complexes
S
–
3
IV.
Initiation Rate Studies
S
–
8
V.
Estimation of
k
-
1
/
k
2
S
–
8
VI.
Evaluation of Selected Catalysts in ROMP
S
–
11
VII.
X
-
Ray
Crystallography Methods
S
–
13
VIII.
Computational Methods
S
–
21
IX.
Cartesian Coordinates of Optimized Catalyst Structures
S
–
21
X.
1
H and
13
C NMR Spectra
S
–
42
XI.
References
S
–
56
I. G
eneral Information
Solvents were dried by passing through an activated alumina column (
n
-
pentane,
benzene, toluene, Et
2
O, and THF). Deuterated solvents were purchased from Cambridge
Isotopes Laboratories, Inc. and were degassed and stored over activated 3 Å molecular
sieves prior to use. C
6
D
6
was purified by passage through a solvent purifica
tion column.
Ethyl vinyl ether was degassed with argon or nitrogen gas prior to use.
Amines were
distilled prior to use.
Catalyst
G2
was obtained from Materia, Inc. The bispyridine
complex
G3
was synthesized according to literature procedure.
1
All reactions were
carried out in dry glassware under a
nitrogen
atmosphere unless otherwise indicated.
NMR spectra were measured with Varian 500 MHz, Varian 400 MHz, and Bruker
400 MHz spectrometers. High
-
resolution mass spectra (HRMS) were provided by
the
S
–
2
California Institute of Technology Mass Spectrometry Facility using a JEOL JMS
-
600H
High Resolution Mass Spectrometer.
SEC data were collected using two Agilent PLgel MIXED
-
B 300 × 7.5 mm columns
with 10 μm beads, connected to an Agilent 1260 Series
pump, a Wyatt 18
-
angle DAWN
HELEOS light scattering detector, and Optilab rEX differential refractive index detector.
The mobile phase was THF.
The crystallographic measurements were performed at 100(2) K using a Bruker
APEX
–
II CCD area detector diffractom
eter (Mo
-
K
a
radiation,
l
= 0.71073 Å). In each case,
a specimen of suitable size and quality was selected and mounted onto a nylon loop. The
structures were solved by direct methods, which successfully located most of the non
-
hydrogen atoms. Semi
-
empirical
absorption corrections were applied. Subsequent
refinement on
F
2
using the SHELXTL/PC package (version 6.1) allowed location of the
remaining non
-
hydrogen atoms.
II.
Preparation of Aminosphosphine Ligands
Amino
phosphine ligands were synthesized
from the
corresponding
chlorocyclohexylphosphine or PCl
3
according to literature methods.
2
The yields have not
been optimized.
4
-
(D
icyclohexylphosphanyl)morpholine
(L1).
To an
Et
2
O
solution (50 mL) of
Cy
2
PCl (2.300 g, 9.883 mmol)
under a nitrogen atmosphere
was added freshly distilled
morpholine (2.14 mL, 24.7 mmol)
dropwise at ambient temperature. The mixture
immediately became cloudy, and a white precipitate formed. After stirring at room
temperature for one hour, the unwanted white solid was filtered off
u
nder inert
atmosphere
, and the filtrate was subjected to reduced pressures to remove all volatiles
,
affording
L1
as a colorless oil
(2.52 g, 90%).
1
H NMR (300 MHz; C
6
D
6
):
d
3.42 (t, 4H, 4.8 Hz), 2.84
–
2.80 (m, 4H), 1.80
–
1.51 (m,
11H), 1.25
–
1.16 (m, 1
1H).
31
P{
1
H}
NMR (121 MHz; C
6
D
6
):
d
75.6 (s)
.
N
P
O
S
–
3
III. P
reparation
of Aminophosphine
-
Ligated Complexes
Note:
Following the course of the reaction in THF, removal of volatiles occasionally
resulted in some remaining bright green solid indicating unreacted
G3
. In this case, the
residue was redissolved in 2 mL of THF and stirred for another 2 min
, and the volatiles
once again removed; t
his was repeated until
there was no indication of
unreacted
G3
.
The yields have not been optimized.
Catalyst 1
.
To a THF solution (2 mL) of the bispyridine complex
G3
(150 mg, 0.206
mmol), was added 2.5 equivalent
s
(146 mg, 0.516 mmol) of the appropriate phosphine
ligand, 4
-
(dicyclohexylphosphanyl)morpholine in THF (1 mL). The resulting mixture was
stirred at room temperature for 20 min. All volatiles were then removed under reduced
pressure. Addition of pentane led
to the formation of a pink precipitate of the desired
complex,
1
,
which was isolated by filtration through celite and dried under vacuum (129
mg, 73%). Dark brown crystals were obtained by slow Et
2
O vapor diffusion into a THF
solution of the title complex
.
1
H NMR
(500 MHz; C
7
D
8
):
d
19.51 (s, 1H), 9.14 (bs, 1H), 7.18
–
7.10 (m, 2H), 6.98
–
6.83 (m, 4H), 6.23 (bs, 2H), 3.61
–
3.17 (m, 9H), 2.76 (s, 6H), 2.65
–
2.25 (m, 10H), 2.21 (s, 3H),
1.79 (s, 3H), 1.70
–
1.39 (m, 11H), 1.23
–
0.98 (m, 8H), 0.76 (d,
J
=
12.5 Hz, 2H)
.
13
C NMR
(101 MHz; C
6
D
6
):
d
296.25, 220.71 (d,
2
J
C
-
P
= 84.8 Hz), 151.99, 139.39, 138.61,
137.63, 137.23, 135.59, 130.31, 129.39, 68.02, 52.11, 51.08, 49.37, 35.39 (d,
J
C
-
P
= 19.6 Hz), 29.18,
28.74, 28.02, 27.93, 27.84, 27.72, 26.59, 21.23, 2
1.03, 20.57, 19.00
.
31
P{
1
H}
NMR (162 MHz;
C
6
D
6
):
d
92.4 (s).
MS (FAB)
m/z
(M
+
+H) calcd for
C
44
H
63
ON
3
RuPCl
2
: 852.3130, found: 852.3153.
Ru
P
Cl
Cl
N
N
Ph
O
N
S
–
4
Catalyst 2
.
To a THF solution (2 mL) of the bispyridine complex
G3
(100 mg, 0.138
mmol), was added 1.2 equivalent (47 mg, 0.165 mmol) of the appropriate phosphine ligand,
4,4’
-
(cyclohexylphosphanediyl)dimorpholine in THF (1 mL). The resulting mixture was
stirred at room temperature for 20 min. All volatiles were then rem
oved under reduced
pressure. Addition of pentane led to the formation of a pink precipitate of the desired
complex,
2
,
which was isolated by filtration through celite and dried under vacuum (79
mg, 67%).
1
H NMR
(400 MHz; C
6
D
6
):
d
19.40 (s, 1H),
8.17 (bs,
2H), 7.12 (t,
J
= 7.6 Hz, 1H), 7.06
(s, 2H), 6.93 (t,
J
= 7.6 Hz, 2H), 6.21 (bs, 2H), 3.50
–
3.21 (m, 12H), 3.09 (t,
J
= 12.3 Hz, 1H),
2.86 (bs, 9H), 2.66
–
2.40 (m, 13H), 1.79 (s, 3H), 1.67
–
1.51 (m, 6H), 1.17
–
1.10 (m, 2H), 0.99
(tt,
J
= 12.6 Hz,
J
=
3.5 Hz, 1H), 0.77 (q,
J
= 12.4 Hz, 2H)
.
13
C NMR
(101 MHz; C
6
D
6
):
d
293.55, 221.10 (d,
2
J
C
-
P
= 89.0 Hz), 151.59, 139.44, 139.26,
137.69, 137.49, 136.93, 135.03, 131.06, 130.55, 129.37, 67.64, 52.14, 50.97, 47.16, 37.38 (d,
J
C
-
P
=
23.7 Hz), 27.66, 27.48, 27.36, 27.25, 21.23, 21.00, 20.63, 18.92
.
31
P{
1
H}
NMR (161.8 MHz;
C
6
D
6
):
d
131.9 (s).
MS (FAB)
m/z
(M
+
) calcd for
C
42
H
59
O
2
N
4
RuPCl
2
: 854.2797, found: 854.2834.
Catalyst 3
.
To a THF solution (2 mL) of the bispyridine complex
G3
(173 mg, 0.238
mmol), was added 1.2 equivalent (82 mg, 0.286 mmol) of the appropriate phosphine ligand,
trimorpholinophosphane in THF (1 mL). The resulting mixture was stirred at room
temperature for 2
0 min. All volatiles were then removed under reduced pressure. Addition
of pentane led to the formation of a pink precipitate of the desired complex,
3
,
which was
isolated by filtration through celite and dried under vacuum (157 mg, 77%).
Ru
P
Cl
Cl
N
N
Ph
N
O
O
N
Ru
P
Cl
Cl
N
N
Ph
N
O
N
O
O
N
S
–
5
1
H NMR
(500 MHz
; C
7
D
8
):
d
19.44 (s, 1H), 8.03 (s, 2H), 7.12 (s, 1H), 6.93
–
6.85 (m,
4H), 6.16 (s, 2H), 3.46
–
3.37 (m, 2H), 3.33
–
3.21 (m, 14H), 2.75 (s, 6H), 2.68 (q,
J
= 4.7 Hz,
12H), 2.35 (s, 6H), 2.28 (s, 3H), 1.77 (s, 3H)
.
13
C NMR
(101 MHz; C
6
D
6
):
d
298.46, 219.58 (d,
2
J
C
-
P
= 107.3 Hz), 151.81, 139.51, 139.07,
137.61, 137.52, 137.09, 135.33, 130.95, 130.24, 129.40, 128.80, 128.59, 67.60 (d,
J
C
-
P
= 5.8 Hz),
51.90 (d,
J
C
-
P
= 4.7 Hz), 50.91 (d,
J
C
-
P
= 2.9 Hz), 46.86 (d,
J
C
-
P
= 3.0 Hz), 21.14, 20.97, 20.6
5, 18.92
.
31
P{
1
H}
NMR (162 MHz;
C
6
D
6
):
d
116.7 (s).
MS (FAB)
m/z
(M
+
) calcd for
C
40
H
56
O
3
N
5
RuPCl
2
: 857.2542, found: 857.2517.
Catalyst 4
.
To a THF solution (2 mL) of the bispyridine complex
G3
(100 mg, 0.138
mmol), was added 1.2 equivalent (46.5 mg, 0.165 mmol) of the appropriate phosphine
ligand, 1
-
(dicyclohexylphosphanyl)piperidine in THF (1 mL). The resulting mixture was
stirred at room temperature for 20 min. All volatiles were then removed
under reduced
pressure. Addition of pentane led to the formation of a pink precipitate of the desired
complex,
4
,
which was isolated by filtration through celite and dried under vacuum (93
mg, 80%). Dark brown crystals were obtained by slow Et
2
O vapor dif
fusion into a benzene
solution of the title complex.
1
H NMR
(400 MHz; C
6
D
6
):
d
19.70 (s, 1H), 9.37 (bs, 1H), 7.19
–
7.12 (m, 2H), 7.06
–
6.89 (m,
4
H), 6.80
–
5.56 (m, 2H), 3.50
–
3.14 (m, 5H), 3.08
–
2.75 (m, 7H), 2.73
–
2.55 (m, 7H),
2.21 (s, 3H), 1.82 (s, 3H), 1.79
–
1.04 (m, 26H), 0.95
–
0.77 (m, 2H).
13
C NMR
(101 MHz; C
6
D
6
):
d
296
.05, 221.10
(d,
2
J
C
-
P
= 83.5 Hz)
, 152.07, 139.43, 138.29,
137.75,
137.54, 137.27, 135.87, 130.29, 129.39, 52.19, 51.10, 50.31, 35.88
(d,
J
C
-
P
= 19.9 Hz)
, 29.31,
28.86, 28.12, 28.03, 27.94, 27.81, 27.45, 27.40, 26.68, 25.18, 21.14
(d,
J
C
-
P
= 18.0 Hz)
, 20.60, 19.07.
31
P{
1
H}
NMR (161.8 MHz;
C
6
D
6
):
d
92.1 (s).
MS (FAB)
m/z
(M
+
) calcd for
C
45
H
64
N
3
RuPCl
2
: 849.3259, found: 849.3267.
Ru
P
Cl
Cl
N
N
Ph
N
S
–
6
Catalyst 5
.
To a THF solution (2 mL) of the bispyridine complex
G3
(
130 mg, 0.179
mmol), was added 4
.2 equivalent (210 mg, 0.744 mmol) of the appropriate phosphine
ligand, 1,1’
-
(cyclohexylphosphanediyl)dipiperidine in THF (1 mL). The resulting mixture
was stirred at room temperature for 20 min. All volatiles were then removed under
reduced pressure. Addi
tion of pentane led to the formation of a pink precipitate of the
desired complex,
5
,
which was isolated by filtration through celite and dried under vacuum
(82 mg, 54%). Dark brown crystals were obtained by slow Et
2
O vapor diffusion into a THF
solution of
the title complex.
1
H NMR
(400 MHz; C
6
D
6
):
d
19
.47 (s, 1H), 8.46 (bs, 1H), 7.19
–
7.13 (m, 2H), 7.01 (t,
J
= 7.7 Hz, 2H), 6.94 (s, 2H), 6.77
–
5.44 (m, 2H), 3.44
–
3.17 (m, 4H), 3.04
–
2.75 (m, 11H), 2.75
–
2.56 (s, 6H), 2.22 (s, 3H), 1.82 (s, 3H), 1.69
–
1.50 (m, 5H), 1.41 (s, 11H), 1.28 (s, 7H), 1.08
–
0.75 (m, 3H).
13
C NMR
(101 MHz; C
6
D
6
):
d
291.90, 222.33
(d,
2
J
C
-
P
= 87.8 Hz)
, 151.79, 139.65, 138.08,
137.96, 137.35, 136.97, 135.91, 131.17, 130.35, 129.36, 52.34, 52.30, 50.97, 47.68, 38.15
(d,
J
C
-
P
=
23.9 Hz)
, 27.80, 27.63, 27.50, 27.16, 27.11, 25.77, 25.22, 21.12
(d,
J
C
-
P
= 12.9 Hz)
, 20.64, 19.07.
31
P{
1
H}
NMR (161.8 MHz;
C
6
D
6
):
d
133.0 (s).
MS (FAB)
m/z
(M
+
) calcd for
C
44
H
63
N
4
RuPCl
2
: 850.3211, found: 850.3212.
Catalyst 6
.
To a THF solution (2 mL) of the bispyridine complex
G3
(100 mg, 0.138
mmol), was added 1.5 equivalent (58.7 mg, 0.207 mmol) of the appropriate phosphine
ligand, tri(piperidin
-
1
-
yl)phosphane in THF (1 mL). The resulting mixture was stirred at
room temperature for 20 min. All volatiles were then removed under r
educed pressure.
Addition of pentane led to the formation of a pink precipitate of the desired complex,
6
,
which was isolated by filtration through celite and dried under vacuum (92 mg, 78%). Dark
Ru
P
Cl
Cl
N
N
Ph
N
N
Ru
P
Cl
Cl
N
N
Ph
N
N
N
S
–
7
brown crystals were obtained by slow pentane vapor diffusio
n into a THF solution of the
title complex.
1
H NMR
(400 MHz; C
6
D
6
):
d
19.
70 (s, 1H), 8.30 (bs, 2H), 7.21
–
7.17 (m, 1H), 7.04
–
6.98 (m, 2H), 6.93 (s, 2H), 6.25 (s, 2H), 3.43
–
3.16 (m, 4H), 2.86 (s, 6H), 2.85
–
2.77 (m, 12H),
2.48 (s, 6H), 2.22 (s, 3H),
1.82 (s, 3H), 1.48
–
1.34 (m, 6H), 1.29 (m, 12H).
13
C NMR
(101 MHz; C
6
D
6
):
d
296.09, 221.30 (d,
2
J
C
-
P
= 105.2 Hz), 152.12, 139.67, 138.04,
137.89, 137.38, 137.17, 136.04, 131.22, 130.18, 129.37, 52.07 (d,
J
C
-
P
= 4.9 Hz), 50.94, 47.19 (d,
J
C
-
P
= 4.4 Hz), 27.08 (d,
J
C
-
P
= 4.6 Hz), 25.70, 21.09 (d,
J
C
-
P
= 10.4 Hz), 20.72, 19.10
.
31
P{
1
H}
NMR (161.8 MHz;
C
6
D
6
):
d
118.7 (s).
MS (FAB)
m/z
(M
+
) calcd for
C
43
H
62
N
5
RuPCl
2
: 851.3164, found: 851.3178.
Catalyst 7
.
To a THF solution (2 mL) of the bispyridine complex
G3
(100 mg, 0.138
mmol), was added 2.0 equivalent (73 mg, 0.275 mmol) of the appropriate phosphine ligand,
1
-
(dicyclohexylphosphanyl)
-
1
H
-
pyrrole in THF (1 mL). The resulting mixture was stirred
at room te
mperature for 20 min. All volatiles were then removed under reduced pressure.
Addition of pentane led to the formation of a pink precipitate of the desired complex,
7
,
which was isolated by filtration through celite and dried under vacuum (110 mg, 96%).
Da
rk brown crystals were obtained by slow pentane vapor diffusion into a THF solution
of the title complex.
1
H NMR
(400 MHz; C
6
D
6
):
d
19.82 (s, 1H),
8.24 (bs, 2H), 7.10 (t,
J
= 7.2 Hz, 1H), 6.94
–
6.90 (m, 4H), 6.74 (q,
J
= 2.2 Hz, 2H), 6.21 (s, 4H), 3.36 (dt,
J
= 2.3 Hz,
J
= 10.6 Hz, 2H), 3.23
(dt,
J
= 2.3 Hz,
J
= 10.6 Hz, 2H), 2.81 (s, 6H), 2.44 (s, 6H), 2.19 (s, 3H), 1.80 (s, 3H), 1.63 (d,
J
=
10.8 Hz, 2H), 1.54 (d,
J
= 11.0 Hz, 2H), 1.46
–
1.35 (m, 6H), 1.27 (qt,
J
= 1
2.7 Hz,
J
= 3.4 Hz,
2H), 1.12
–
0.91 (m, 6H), 0.52 (qt,
J
= 12.7 Hz,
J
= 3.4 Hz, 2H).
13
C NMR
(101 MHz; C
6
D
6
):
d
301.30, 219.39 (d,
2
J
C
-
P
= 89.9 Hz), 151.99, 139.40, 138.57,
137.86, 137.37, 137.25, 135.47, 131.50, 130.28, 129.44, 128.97, 128.59, 125.32 (d
,
J
C
-
P
= 2.8 Hz),
110.26 (d,
J
C
-
P
= 4.6 Hz), 52.09 (d,
J
C
-
P
= 4.1 Hz), 51.11 (d,
J
C
-
P
= 2.1 Hz), 35.81 (d,
J
C
-
P
= 18.6 Hz),
28.30 (d,
J
C
-
P
= 4.3 Hz), 27.85 (d,
J
C
-
P
= 2.8 Hz), 27.53, 27.44, 27.40, 27.27, 25.99, 21.25, 21.01,
20.58, 18.95
.
31
P{
1
H}
NMR (162 MHz;
C
6
D
6
):
d
92.3 (s).
MS (FAB)
m/z
(M
+
) calcd for
C
44
H
58
N
3
RuPCl
2
: 831.2789, found: 831.2761.
Ru
P
Cl
Cl
N
N
Ph
N
S
–
8
IV
. Initiat
ion Rate Studies
In a nitrogen
-
filled glovebox, t
he
ruthenium
benzylidene complex was dissolved
in toluene
-
d
8
(600
μ
L, 0.017 M) in an NMR tube fitted with a septum cap.
The sealed NMR
tube was relocated near the NMR spectrometer.
To this NMR tube was injected neat ethyl
vinyl ether (30 equiv.) us
ing a glass
syringe under inert atmosphere. The tube was
inverted
twice
and immediately loaded into a 500 MHz
1
H NMR spectrometer pre
-
warmed to 30 °C, at which point the first
-
order depletion of the benzylidene Ru=C
H
Ph
signal was monitored.
Plotting ln([Ru]
0
/[Ru]
t
) vs. time provided the initiation rate
constant.
V. E
stimation of
k
-
1
/
k
2
In a nitrogen
-
filled glovebox, a
solution of toluene
-
d
8
(600
μ
L) containing the
ruthenium
benzylidene complex (0.017 M) and free aminophosphine ([P]/[ethyl vinyl
ether] = 0.6, 1.0, 1.6
; mass of phosphine calculated based upon 15
μ
L
ethyl vinyl ether
)
was added to an NMR tube fitted with a septum cap.
The sealed NMR tube was relocated
near the NMR spectrometer.
To this NMR tube was injected neat ethyl vinyl ether (15
μ
L
)
using a glass
syringe under inert atmosphere. The tube was inver
ted
twice
and
immediately loaded into a 500 MHz
1
H NMR spectrometer pre
-
warmed to 30 °C, at which
point the first
-
order depletion of the benzylidene Ru=C
H
Ph signal was monitored.
In
order to determine
k
obs
, the data from each array with a specific [P]/[eth
yl vinyl ether]
ratio
were analyzed in th
e same way as described above in
the initiation rate studies.
Due
to poor solubility of the aminophosphine in toluene, the experiment for catalyst
3
and
ligand
L3
was performed with [Ru]
0
= 0.005 M
and 4.4
μ
L
ethyl
vinyl ether
.
The values of 1/
k
obs
were plotted vs. [P]/[ethyl vinyl ether], including the data from
initiation rate studies where [P]/[olefin] = 0. The graph for each catalyst is shown below.
The ratio of
k
-
1
/
k
2
was calculated by dividing the slope of the
line of best fit by the y
-
intercept.
S
–
9
Catalyst 1
Catalyst 2
y = 333.6x + 231.45
R² = 0.99974
0
100
200
300
400
500
600
700
800
900
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
1/kobs
[P]/[olefin]
y = 241.55x + 132.45
R² = 0.99815
0
100
200
300
400
500
600
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
1/kobs
[P]/[olefin]
S
–
10
Catalyst 3
Catalyst 4
y = 2138.9x + 713.34
R² = 0.99567
0
500
1000
1500
2000
2500
3000
3500
4000
4500
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
1/kobs
[P]/[olefin]
y = 172.54x + 245.99
R² = 0.99862
0
100
200
300
400
500
600
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
1/kobs
[P]/[olefin]
S
–
11
Catalyst 5
Catalyst 6
V
I
. E
valuation of Selected Catalysts in ROMP
In a
n
argon
-
filled glovebox, a
solution of
8
(21.0 mg, 0.100 mmol) was prepared in 2
mL of dichloromethane at 298 K. While stirring, the polymerization was initiated by
addition of a CH
2
Cl
2
solution of catalyst (0.0500 M, 20.0 μL, 0.100 μmol). During the course
of the reaction, aliquots (~50 μL) wer
e extracted and quenched in separate vials containing
a large excess of ethyl vinyl ether (0.1 mL) in THF (0.9 mL). The quenched reaction mixtures
were analyzed by SEC and
1
H NMR spectroscopy to determine norbornene conversion,
molecular weight (
M
n
), and
dispersity (
Đ
).
y = 181.92x + 317.56
R² = 0.99735
0
100
200
300
400
500
600
700
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
1/kobs
[P]/[olefin]
y = 1150.2x + 1610.4
R² = 0.93965
0
500
1000
1500
2000
2500
3000
3500
4000
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
1/kobs
[P]/[olefin]
S
–
12
Table S.1
. Molecular Weights
and Dispersities of Polymers
9.
Catalyst
M
n
(kDa)
Đ
G2
96.1
1.50
G3
23.1
1.02
4
46.3
1.17
5
55.2
1.22
6
70.1
1.41
7
25.9
1.03
SEC Traces for ROMP Studies
0
0.2
0.4
0.6
0.8
1
12
13
14
15
16
17
18
Normalized dRI
Ret. Vol. (mL)
SEC Traces of ROMP Studies
G3
G2
4
5
6
7
S
–
13
V
I
I.
X
-
Ray Crystallography Methods
3
Table
S.2
. Crystal Data and Structure Analysis Details for
Catalyst 4
.
(Structure shown in Figure
3)
Empirical formula
C100 H144 Cl4 N6 O P2 Ru2
Formula weight
1852.08
Crystal shape
block
Crystal color
brown
Crystal size
0.050 x 0.080 x 0.100 mm
3
Data
Collection
Preliminary photograph(s)
rotation
Type of diffractometer
CCD area detector
Wavelength
0.71073
Å
Data collection temperature
100(2) K
Theta range for 9838 reflections used
in lattice determin
ation
4.655 to 65.411
°
Unit
cell dimensions
a =
12.5478(5) Å
a
= 90
°
b = 14.1495(6) Å
b
= 92.828(2)
°
c = 26.7547(11)
Å
g
= 90
°
Volume
4744.4(3)
Å
3
Z
2
Crystal system
monoclinic
Space group
P 2
1
/
c
Density (calculated)
1.296 g/cm
3
F(000)
1960
Theta range
for data collection
1.6 to 37.7º
Completeness
to theta = 25.242
°
100.0%
Index ranges
-
21
£
h
£
21,
-
24
£
k
£
23,
-
45
£
l
£
45
Reflections collected
180275
Independent reflections
24676 [R
int
= 0.0782]
Reflections > 2s(I)
17555
Average s(I)/(net I)
0.0619
Absorption coefficient
0.51 mm
-
1
Absorption co
rrection
Semi
-
empirical from equivalents
Max. and min. transmission
0.6876 and 0.6876
Structure Solution and Refinement
Hydrogen placement
geom
Refinement method
Full
-
matrix least
-
squares on F
2
S
–
14
Data / restraints / parameters
24676 / 17 / 520
Treatment o
f hydrogen atoms
constr
Goodness
-
of
-
fit on F
2
1.07
Final R indices [I>2s(I), 17555 reflections]
R1 = 0.0561,
w
R2 = 0.1214
R indices (all data)
R1 = 0.0959,
w
R2 = 0.1363
Type of weighting scheme used
calc
Max shift/error
0.001
Average shift/error
0.000
Extinction coefficient
n/a
Largest diff.
peak and hole
2.49 and
-
1.63 e/Å
-
3
Programs Used
Structure refinement
SHELXL
-
2013 (Sheldrick, 2013)
S
–
15
Table S.3
. Crystal Data and Structure Analysis Details for
Catalyst 5
.
(Structure shown in Figure 4
)
Empir
ical formula
C100 H152 Cl4 N8 O3 P2 Ru2 Si0
Formula weight
1920.17
Crystal shape
block
Crystal color
brown
Crystal size
0.020 x 0.150 x 0.150 mm
3
Data Collection
Preliminary photograph(s)
rotation
Type of diffractometer
CCD area detector
Wavelength
0.71073 Å
Data collection temperature
100(2) K
Theta range for 9872 reflections used
in lattice determination
4.877 to 60.270
°
Unit cell dimensions
a = 12.582(4) Å
a
= 90
°
b = 14.694(4) Å
b
=
102.711(9)
°
c = 26.929(9) Å
g
= 90
°
Volume
4856(
3) Å
3
Z
2
Crystal system
monoclinic
Space group
P 2
1
/
n
Density (calculated)
1.313 g/cm
3
F(000)
2036
Theta range for data collection
2.1 to 31.3º
Completeness to theta = 25.242
°
99.9%
Index ranges
-
18
£
h
£
17,
-
21
£
k
£
21,
-
39
£
l
£
39
Reflections c
ollected
109331
Independent reflections
14689 [R
int
= 0.0561]
Reflections > 2s(I)
10910
Average s(I)/(net I)
0.0580
Absorption coefficient
0.51 mm
-
1
Absorption correction
Semi
-
empirical from equivalents
Max. and min. transmission
1.0000 and 0.9533
Structure Solution and Refinement
Hydrogen placement
geom
Refinement method
Full
-
matrix least
-
squares on F
2
Data / restraints / parameters
14689 / 2 / 538
Treatment of hydrogen atoms
constr
S
–
16
Goodness
-
of
-
fit on F
2
1.04
Final R indices [I>2s(I), 10910 refl
ections]
R1 = 0.0645,
w
R2 = 0.1465
R indices (all data)
R1 = 0.1013,
w
R2 = 0.1643
Type of weighting scheme used
calc
Max shift/error
0.001
Average shift/error
0.000
Extinction coefficient
n/a
Largest diff. peak and hole
2.26 and
-
1.25 e/Å
-
3
Programs Used
Structure refinement
SHELXL
-
2013 (Sheldrick, 2013)
S
–
17
Table S.4
. Crystal Data and Structure Analysis Details for
Catalyst 6
.
(Structure shown in Figure 5
)
Empirical formula
C43 H62 Cl2 N5 P Ru
Formula weight
851.91
Crystal shape
block
Crystal color
brown
Crystal size
0.030 x 0.120 x 0.140 mm
3
Data Collection
Preliminary photograph(s)
rotation
Type of diffractometer
CCD area detector
Wavelength
0.71073 Å
Data collection temperature
100(2) K
Theta range for 9656 reflections used
in lattice determination
5.207 to 62.321
°
Unit cell dimensions
a = 12.685(4) Å
a
= 90
°
b = 14.502(4) Å
b
= 99.043(12)
°
c = 22.983(7) Å
g
= 90
°
Volume
4176(2) Å
3
Z
4
Crystal system
monoclinic
Space group
P 2
1
/
c
Density (calculated)
1.355 g/cm
3
F(000)
1792
Theta range for data collection
2.3 to 33.6º
Completeness to theta = 25.000
°
99.9%
Index ranges
-
18
£
h
£
19,
-
22
£
k
£
22,
-
34
£
l
£
30
Reflections collected
100488
Independent reflections
15279 [R
int
= 0.0733]
Reflections > 2s(I)
10188
Average
s(I)/(net I)
0.0882
Absorption coefficient
0.58 mm
-
1
Absorption correction
Semi
-
empirical from equivalents
Max. and min. transmission
0.9954 and 0.9389
Structure Solution and Refinement
Hydrogen placement
geom
Refinement method
Full
-
matrix least
-
squares
on F
2
Data / restraints / parameters
15279 / 138 / 704
Treatment of hydrogen atoms
constr
S
–
18
Goodness
-
of
-
fit on F
2
1.16
Final R indices [I>2s(I), 10188 reflections]
R1 = 0.0820,
w
R2 = 0.1464
R indices (all data)
R1 = 0.1400,
w
R2 = 0.1609
Type of weighting sc
heme used
calc
Max shift/error
0.001
Average shift/error
0.000
Extinction coefficient
n/a
Largest diff. peak and hole
1.13 and
-
1.50 e/Å
-
3
Programs Used
Structure refinement
SHELXL
-
2013 (Sheldrick, 2013)
S
–
19
Table S.5
. Crystal Data and Structure Analysis Details for
Catalyst
7.
(Structure shown in Figure 2
)
Empirical formula
C44 H58 Cl2 N3 P Ru
Formula weight
831.87
Crystal shape
block
Crystal color
brown
Crystal size
0.050 x 0.090 x 0.100 mm
3
Data Collection
Preliminary photograph(s)
rotation
Type of diffractometer
CCD area detector
Wavelength
0.71073 Å
Data collection temperature
100(2) K
Theta range for 9838 reflections used
in lattice determination
4.655 to 65.411
°
Unit cell dimensions
a = 12.1351(9)
Å
a
= 90
°
b = 14.8021(10) Å
b
= 98.642(3)
°
c = 22.944(2) Å
g
= 90
°
Volume
4074.6(6) Å
3
Z
4
Crystal system
monoclinic
Space group
P 2
1
/
c
Density (calculated)
1.356 g/cm
3
F(000)
1744
Theta range for data collection
2.2 to 33.2º
Completeness to theta =
25.242
°
99.9%
Index ranges
-
17
£
h
£
18,
-
21
£
k
£
22,
-
34
£
l
£
34
Reflections collected
125473
Independent reflections
14290 [R
int
= 0.1065]
Reflections > 2s(I)
9560
Average s(I)/(net I)
0.1029
Absorption coefficient
0.59 mm
-
1
Absorption correction
Semi
-
empirical from equivalents
Max. and min. transmission
0.7466 and 0.7034
Structure Solution and Refinement
Hydrogen placement
geom
Refinement method
Full
-
matrix least
-
squares on F
2
Data / restraints / parameters
14290 / 0 / 460
Treatment of hydrogen atoms
constr
S
–
20
Goodness
-
of
-
fit on F
2
1.08
Final R indices [I>2s(I), 9560 reflections]
R1 = 0.0641,
w
R2 = 0.1225
R indices (all data)
R1 = 0.1239,
w
R2 = 0.1426
Type of weighting scheme used
calc
Max shift/error
0.001
Average shift/erro
r
0.000
Extinction coefficient
n/a
Largest diff. peak and hole
2.73 and
-
0.90 e/Å
-
3
Programs Used
Structure refinement
SHELXL
-
2013 (Sheldrick, 2013)
S
–
21
VII
I.
Computational Methods
Geometry optimizations of complexes
G2
,
1
-
3
, and the phosphine ligands
were
performed using M06
4
, with the def2SVP basis set.
5
Single point energies were calculated
using M06 with the def2TZVP basis set. Solvation effects were considered by performing
single point calculations with the SMD model in toluene.
6
All calculations were performed
with Gaussian 09.
7
The reported Gibbs free energies and enthalpies include zero
-
point
vibrational energies and thermal corrections at 298K. The quasiharmonic approximation
from Cramer and Truhlar
8
was applied to compute the
vibrational entropies. In the
quasiharmonic approximation, vibrational frequencies lower than 100 cm
-
1
were raised to
100 cm
-
1
as a way to avoid spurious results associated with the harmonic
-
oscillator model
for very low
-
frequency vibrations.
9
Tolman elec
tronic parameters
10
were calculated with model complex Ni(CO)
3
L
using B3LYP
11
and a mixed basis set of LANL2DZ for Ni and 6
-
31G(d) for other atoms.
12
The computed A
1
stretch frequency was reported with a scaling factor of 0.962.
To reduce computational co
st, structures in the reaction coordinates (Figure 12)
were optimized using B3LYP and a mixed basis set of
SDD
for Ru and 6
-
31G(d) for other
atoms. Single point energies were performed using M06 and a mixed basis set of SDD for
Ru and 6
-
311+G(d,p) for
other atoms.
I
X. Cartesian Coordinates of Optimized Catalyst Structures
Catalyst G2
M06/def2SVP SCF energy:
-
3255.08587815 a.u.
M06/def2SVP enthalpy:
-
3254.017016 a.u.
M06/def2SVP free energy:
-
3254.155540 a.u.
M06/def2TZVP SCF energy in solution:
-
3257.59943330 a.u.
M06/def2TZVP enthalpy in solution:
-
3256.530571 a.u.
M06/def2TZVP free energy in solution:
-
3256.669095 a.u.
Cartesian coordinates
ATOM X Y Z
Ru 0.038148
-
0.408366 0.132840
Cl
-
0.213729
-
0.507936
-
2.285132
Cl
-
0.231280
-
0.403305 2.557522
P
-
0.986221 1.836871 0.114061
C 0.380184
-
2.437817 0.230718
N 1.551204
-
3.088272 0.421064
C 1.376149
-
4.526015 0.644494
H 1.577486
-
4.77
6237 1.702450