Synthesis and reactivity of phosphine-arenesulfonate palladium(II) alkyl complexes that contain methoxy substituents

Article abstract of DOI:10.1016/j.jorganchem.2019.06.012

Phosphine-arenesulfonate ligands that contain 1-3 methoxy substituents on the benzo linker, P(2-OMe-Ph)₂(2-SO₃Na-5-OMe-Ph) (Na[1a]), P(2-MeO-Ph)₂(2-SO₃Na-4,5-(OMe)₂-Ph) (Na[1b]) and P(2-MeO-Ph)_2<

Full text of DOI:10.1016/j.jorganchem.2019.06.012

Accepted Manuscript
Synthesis and reactivity of phosphine-arenesulfonate Palladium(II) alkyl complexes
that contain methoxy substituents
Qian Liu, Richard F. Jordan
PII:
S0022-328X(19)30251-7
DOI:
https://doi.org/10.1016/j.jorganchem.2019.06.012
JOM 20824
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 14 May 2019
Revised Date: 11 June 2019
Accepted Date: 12 June 2019
Please cite this article as: Q. Liu, R.F. Jordan, Synthesis and reactivity of phosphine-arenesulfonate
Palladium(II) alkyl complexes that contain methoxy substituents, Journal of Organometallic Chemistry
(2019), doi: https://doi.org/10.1016/j.jorganchem.2019.06.012.
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ACCEPTED MANUSCRIPT
Synthesis and Reactivity of Phosphine-arenesulfonate Palladium(II) Alkyl Complexes that
Contain Methoxy Substituents
Qian Liu and Richard F. Jordan*
Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, Illinois
6
0637, United States
Key words
Palladium, phosphine-arenesulfonate, ethylene polymerization, vinyl fluoride copolymerization
Abstract
Phosphine-arenesulfonate ligands that contain 1-3 methoxy substituents on the benzo linker, P(2-
OMe-Ph)
2
(2-SO
3
2 3 2
Na-5-OMe-Ph) (Na[1a]), P(2-MeO-Ph) (2-SO Na-4,5-(OMe) -Ph) (Na[1b])
and P(2-MeO-Ph)
2
(2-SO Li-3,4,5-(OMe) -Ph) (Li[1c]) were synthesized and isolated in 52-85 %
3
3
yield. Reaction of Na[1a,b] and Li[1c] with (COD)PdMeCl and pyridine generates the
corresponding (PO)PdMe(pyridine) complexes 2a-c. 2a and 2b were isolated in crystalline form
in 59 % and 86 % yield, respectively, while 2c decomposed during attempted isolation. 2a,b
polymerize ethylene to linear polyethylene and copolymerize ethylene with vinyl fluoride (VF)
to linear copolymer with ca. 0.5 mol % VF incorporation.
1
. Introduction
Palladium alkyl complexes that contain phosphine-arenesulfonate ligands ((PO)PdRL, A,
Chart 1) polymerize ethylene to linear polyethylene (PE) and copolymerize ethylene with a wide
range of polar CH =CHX vinyl monomers (e.g. X = CO R, OR, OAr, CN, F).[1,2] However,
PO)PdRL catalysts usually exhibit lower activity and produce PEs with lower molecular
2
2
(
1

ACCEPTED MANUSCRIPT
weights (MWs) compared to other single-site catalysts.[3] Moreover, the catalyst performance is
further compromised by the polar monomers, which can function as inhibitors, poisons and chain
transfer agents.
-
Electronic modifications of the PR2 groups on the PO ligands have been explored in order to
improve the performance of (PO)PdRL catalysts.[4] Claverie and co-workers studied a series of
(
PO)PdRL complexes with a range of −PAr , −P(alkyl) and −PAr(alkyl) units (A, L = pyridine
2 2
or lutidine, Chart 1)[4b] and found a strong positive correlation between the phosphine donor
ability and the ethylene polymerization activity. Mecking and coworkers investigated the
2
electronic effects of para substituents (R') on the PAr rings of catalysts of type B (L = dmso,
Chart 1) on ethylene polymerization.[4a] Catalysts with electron-donating R' substituents
generally exhibited slightly lower productivity but produced PE with higher MW compared to
−
1
catalysts with electron-withdrawing R' substituents (e.g. R' = OMe: productivity = 1344 kg mol
−1, M = 19,000 vs. R' = CF : productivity = 2016 kg mol h−1, M = 10,100). Modifications of
−1
h
n 3 n
-
the benzo linker within the PO ligand have also been explored.[5] Incorporation of an electron-
donating Me group para to the sulfonate group in (o-PPh SO )PdMe(py) results in lower
2
-
C
6
H
4
3
ethylene polymerization activity but does not affect the MW of the PE product significantly.[5a]
Replacement of the benzo linker that connects the phosphine and sulfonate units in A with a 1,2-
naphthalene linker increases the ethylene polymerization activity 2 to 10-fold but has only a
minor effect on the MW of the PE that is produced.[5b]
The present work is focused on (PO)PdMe(py) catalysts of type A that contain methoxy
substituents on the benzo ring that links the phosphino and sulfonate groups. The motivation for
this work was twofold. First, we were interested to probe how the incorporation of such
substituents influence catalyst performance. A methoxy group is electron-donating to the ortho
2

ACCEPTED MANUSCRIPT
and para positions through the resonance effect (σpara = -0.27) and electron-withdrawing from
the meta positions through the inductive effect (σmeta = 0.12). Second, we recently reported that
-
(
OPO-Li)PdMeL complexes based on the phosphine-bisarenesulfonate ligand PPh(2-SO -4,5-
3
2
-
(
OMe) -Ph) (OPO ), which contains two methoxy groups on each benzo linker, self-assemble
2
2
into Pd species that are held together by a Li S O •Li Cl cage (C, Chart 1).[6] These Pd
4
4
4
12
2
2
species function as single-site catalyst for the polymerization of ethylene to high-molecular
weight PE (M = 640,000, PDI = 2.3) in hexanes suspension. Studies of mononuclear analogues
n
are of interest for understanding the origins of this behavior.
We report the synthesis of three new ligands (1a-c, Scheme 2.1) that contain 1-3 methoxy
groups on benzo linker and the corresponding (PO)PdMe(py) complexes. The ethylene
polymerization and ethylene/vinyl-fluoride (VF) copolymerization behavior of these complexes
is also discussed.
Chart 1. (PO)PdR complexes. py’ = 4-(5-nonyl)-pyridine. L = py, dmso or other neutral ligand.
The lower (Li-OPO)PdMe(py’) units in the schematic structure of C are denoted by “Pd”.
R
R
py'
Me
py'
Me
P
Me
L
Pd
Pd
Pd
Ph
X
X
O
Ph
O
O
X
S
O
P
O
P
S
X
S
O
O
O
O
S
O
Li
O
A
O
O
Li
S
O
O
MeO OMe
MeO OMe
O
R'
Li
S
Cl
R'
Cl
Li
MeO
O
Li
OMe
Me
O
Pd
O
P
O
Pd
Li
O
S
S
O
L
O
Pd
O
B
C, X = OMe
3

ACCEPTED MANUSCRIPT
2
. Results and Discussion
.1 Synthesis of Na[1a-b] and Li[1c]. The synthetic route used to prepare the new ligands
2
studied here is shown in Scheme 1. The appropriate methoxy-substituted aryl lithium reagents
were generated by ortho-lithiation or lithium-halogen exchange of the corresponding arene or
i
n
arylbromide 3a-c- Bu with BuLi, and reacted with P(2-OMe-Ph) Cl to afford pro-ligands 1a-c-
2
i
i
i
Bu.[7] 1a-c- Bu were purified by chromatography and isolated in 30-49 % yield. 1a- Bu and 1b-
i
+
Bu were converted to the corresponding Na sulfonate salts Na[1a,b] by reaction with NaI in
CH CN. Na[1a,b] precipitated from the reaction mixture and were isolated by filtration in 57-85 %
3
3
yield. Na[1c] was generated in an analogous manner but is soluble in CH CN and thus is difficult
to separate from the excess NaI used in the reaction. Therefore, Li[1c] was generated by reaction
i
of 1c- Bu with LiI in CH
3
CN and isolated in 52 % yield.
Scheme 1. Synthesis of Na[1a-b] and Li[1c]. Ar = 2-OMe-Ph.
4

ACCEPTED MANUSCRIPT
2
.2 Synthesis of Methoxy-Substituted (PO)PdMe(py) Complexes. The reaction of
Na[1a,b] with (COD)PdMeCl and pyridine in CH Cl generated a clear yellow solution of 2a-b
2
2
(
Scheme 2). 2a,b were isolated by layering pentane onto the CH Cl solution to give X-ray
2 2
quality crystals in 59-86 % yield. The synthesis of 2c by this route was unsuccessful. The
reaction of Li[1c] with (COD)PdMeCl and pyridine in CH Cl gave a cloudy solution, and the
2
2
formation of Pd black was observed upon attempted isolation of the product.
Scheme 2. Synthesis of 2a,b. Ar = 2-OMe-Ph.
i
An alternative metalation procedure was explored that involves the direct reaction of 1c- Bu
with (COD)PdMeCl and pyridine (Scheme 3). This reaction results in the clean generation of 2c,
which was characterized by NMR. However 2c could not be isolated in pure form due to
apparent thermal decomposition. It is likely that this metalation process proceeds by initial
2
i
formation of [κ -P,O-(1c- Bu)]PdMeCl, displacement of chloride by pyridine, and nucleophilic
-
i
i
attack of the free Cl on the activated Bu group to form 2c and BuCl, as shown in Scheme 3. 2b
was synthesized by this route on a preparatory scale.
5

ACCEPTED MANUSCRIPT
Scheme 3. Synthesis of 2b,c by direct metalation of 1b,c. Ar = 2-OMe-Ph
Ar
OMe
MeO
R4
Ar
(
COD)PdMeCl
R4
R3
CH Cl
2
2
P
Me
Pd
PAr2
R3
S
O
Cl
i
SO Bu
O
i
3
O Bu
i
3
4
1
1
b- Bu R = H, R = OMe
py - iBuCl
i
3
4
c- Bu R = R = OMe
MeO
R4
Ar
Ar
P
Me
py
Pd
R3
S O
O
O
3
4
2
2
b R = H, R = OMe
3
4
c R = R = OMe
2
.3 X-ray crystallography. The solid-state structures of 2a,b were determined by X-ray
2
-
crystallography and are shown in Figures 1 and 2. In each case, κ -P,O coordination of the PO
ligand and a cis relationship of the phosphine and methyl group are observed. The six-membered
(PO)Pd chelate rings adopt boat conformations. The Pd-C distances in 2a (2.022(2) Å) and 2b
2
(
2.0237(18) Å) are very similar to that in {κ -P,O-P(2-OMe-Ph) (2-SO -Ph)}PdMe(py) (4, Chart
2
3
2
, 2.028 Å), the analogue of 2a,b that lacks methoxy substituents on the benzo linker.[8] The Pd-
P distance in 2a (2.2368(5) Å) is slightly longer than that in 2b (2.2234(4) Å), which may be due
to the electron donating effect of the second methoxy group that is para to the phosphine in 2b.
The solution NMR data for 2a,b are consistent with the solid-state structures. Both 2a and 2b
3
2
exhibit J
values ≤3 Hz and J
values ≤4 Hz, indicating a cis relationship of the
P-CH3
P-CH3
phosphine and methyl groups.
6

ACCEPTED MANUSCRIPT
Figure 1. Molecular structure of 2a. Hydrogen atoms are omitted. Atom color scheme: C: grey;
O: red; P: orange; S: yellow; N: blue; Pd: teal. Selected bond lengths (Å) and angles (deg): Pd1-
P1 2.2368(5), Pd1-O1 2.1618(13), Pd1-N1 2.1535(15), Pd1-C1 2.022(2), O1-S1 1.4834(14), O1-
Pd1-P1 94.09(4), N1-Pd1-P1 174.86(4), N1-Pd1-O1 87.07(5), C1-Pd1-P1 87.37(6), C1-Pd1-O1
1
76.32(7), C1-Pd1-N1 91.77(7).
Figure 2. Molecular structure of 2b. Hydrogen atoms are omitted. Atom color scheme: C: grey;
O: red; P: orange; S: yellow; N: blue; Pd: teal. Selected bond lengths (Å) and angles (deg): Pd1-
P1 2.2234(4), Pd1-O1 2.1768(11), Pd1-N1 2.1189(13), Pd1-C1
2.0237(18),
.4840(11), O1-Pd1-P1 94.88(3), N1-Pd1-P1 175.96(4), N1-Pd1-O1 88.92(5), C1-Pd1-P1
6.83(5), C1-Pd1-O1 177.78(7), C1-Pd1-N1 89.41(6).
S1-O1
1
8
7

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Chart 2. Structures of (PO)PdMe(py) complexes 4 and 5.
2
.4 Ethylene Homopolymerization. The ethylene polymerization behavior of 2a,b is
summarized and compared to that of the benchmark catalyst 4 in Table 1. In toluene solvent at 80
o
-1 -1
C, 2a,b display activities in the range 450-515 kgómol-Pd óh (entries 1,2,7,8), similar to that
of 4 (entry 13).[4b,9] The main difference in the performance of these catalysts is that 2a,b
produce PE with lower MW (M = 25-30 kDa) compared to 4 (M = ca. 50 kDa). 2a,b both
w
w
exhibit higher activity with lower catalyst loading (Table 1, entry 1 and 2 vs. 5 and 6; 7 and 8 vs.
1 and 12). Possible explanations for this observation include mass transport effects, bimolecular
1
catalyst decomposition, and a greater extent of pyridine dissociation at lower catalyst
concentrations. The activity and polymer MWs for 2a,b observed for polymerizations in hexane
suspension are lower than in toluene solution. Highly linear PE is formed in all cases.
8

ACCEPTED MANUSCRIPT
Table 1. Homopolymerization of ethylene by 2a and 2b.
c
c
d
Entry
Cat.
Pd
Solvent Yield
(g)
Activity
Mw
PDI
Tm
(°C)
-1
-1
3
(
µmol)
(kgó
mol
ó
h ) (10 )
a
1
2
3
4
2a
2a
2a
2a
2a
10
10
10
10
toluene
toluene
8.92
9.89
446
494
157
158
869
29.6
29.9
29.7
30.4
2.0 136.3
1.8 134.8
2.1 132.0
2.6 132.4
1.7 135.1
a
a
hexanes 3.14
hexanes 3.16
toluene/ 1.53
PhCl
a
a,b
5
0.88
29.7
a,b
6
2a
0.88
toluene/ 1.73
983
27.5
1.8 134.5
PhCl
toluene
toluene
hexanes 1.24
hexanes 1.22
toluene/ 2.57
PhCl
a
7
8
9
1
2b
2b
2b
2b
2b
10
10
10
10
0.88
10.3
10.1
515
505
62.0
60.9
1462
26.1
25.6
18.8
19.1
27.0
1.8 134.5
1.7 135.4
2.3 131.2
2.3 131.8
1.8 135.1
a
a
a
0
a,b
1
1
a,b
1
2
2b
0.88
toluene/ 2.05
1164
27.7
1.6 135.1
PhCl
toluene
toluene
e
1
1
3
4
4
20
10
9.97
2.1
498
210
46.6
51.0
2.5
2.8 129.0
134
f
4
a
b
Conditions: 410 psi C
2
H
4
, 80 ˚C, 2 h, 50 mL solvent. Solvent = 49 mL toluene + 1 mL
chlorobenzene; catalyst added to the reactor as a stock solution in chlorobenzene to facilitate
c
d
e
accurate control of catalyst loading. Determined by GPC. Determined by DSC. ref 9.
f
Conditions: 580 psi C H , 80 ˚C, 1 h, 100 mL toluene. ref 4b. Conditions: 300 psi C H , 85
2
4
2
4
˚C, 1 h, 200 mL toluene.
2
.5 Ethylene/Vinyl Fluoride Copolymerization. Complexes 2a,b copolymerize ethylene
and VF to low-MW copolymer with ca. 0.5 mol % VF incorporation (Table 2). The catalyst
activity is strongly depressed and the copolymer MWs are lower compared to the results of
ethylene homopolymerization reactions, as observed for other (PO)PdRL catalysts.[2o,p, 10] The
1
9
1
microstructure of copolymers produced by 2a,b was determined by F{ H} NMR (Figure 3) and
1
H NMR spectroscopy (See SI).[2o,p,10,11] VF is incorporated primarily as in-chain -
CH CHFCH - units. Chain-end -CH CFHCH , -CH CF H, and -CH CFH units are also present
2
2
2
3
2
2
2
2
in lower amounts. The -CH
2
CFHCH
3
chain ends are most likely formed by β-H elimination to
9

ACCEPTED MANUSCRIPT
2 2 2 2
generate a (PO)Pd-H species, followed by 2,1 VF insertion. The -CH CF H and -CH CFH chain
ends are most likely formed by β-F elimination to generate a (PO)Pd-F species, followed by 1,2
VF insertion or ethylene insertion and subsequent chain growth.[11] An alternative source of the
2 2
-CH CFH chain ends is 1,2 VF insertion into the (PO)Pd-H species. The ethylene/VF
copolymerization results for 2a,b and the copolymer microstructures are very similar to results
2
for {κ -P,O-P(2-OMe-Ph)
2
(2-SO
3
-5-Me-Ph)}PdMe(py) (5, Chart 1), which contains a methyl
substituent para to the sulfonate group on the bezno linker.[11]
Table 2. Ethylene/Vinyl Fluoride Copolymerization by 2a and 2b.
c
c
d
e
Entr Cat. Yiel
Activity
M
w
PDI VF incorp
T
m
-1
-
y
d
(kg·mol ·h
(mol %)
(°C)
1
3
(
mg)
)
(10 )
a
1
2
3
2a
2b
5
115
102
90
5.8
5.1
4.5
13.5 2.3
12.1 2.0
15.0 1.9
0.59
0.51
0.48
131.4
131.4
131.6
a
a,b
a
Conditions: 220 psi ethylene, 80 psi VF, [Pd] = 10 b
µmol, temperature = 80 ˚C, time = 2 h,
c
d
solvent = 40 mL toluene + 10 mL chlorobenzene. ref 10. Determined by GPC. VF
incorporation in copolymer determined by H NMR. Determined by DSC.
1
e
1
9
1
Figure 3. F{ H} NMR spectrum of ethylene/VF copolymer (o-dichlorobenzene-d , 100 °C)
4
produced by 2b (Table 2, entry 2). P = polymeryl.
10

ACCEPTED MANUSCRIPT
3
. Conclusions
The phosphine-arenesulfonate ligands Na[1a-b] and Li[1c], which contain 1-3 methoxy
substituents on the arenesulfonate rings, have been synthesized. Na[1a,b] and Li[1c] react with
COD)PdMeCl to form (PO)PdMe(pyridine) complexes 2a-c, however 2c decomposed during
(
attempted isolation. The structures of 2a,b have been analyzed by X-ray crystallography. 2a,b
polymerize ethylene to linear PE and copolymerize ethylene with VF to linear copolymer with ca.
0
.5 mol% VF incorporation. Catalysts 2a,b exhibit similar polymerization behavior compared to
the benchmark catalysts 4 and 5, indicating that the methoxy groups have only a modest
influence on the reactivity.
4
. Experimental Section
.1 General Procedures. All experiments were performed under a nitrogen atmosphere
using drybox or Schlenk techniques. Nitrogen was purified by passage through Q-5 oxygen
4
11

ACCEPTED MANUSCRIPT
scavenger and activated molecular sieves. Methylene chloride, diethyl ether and THF were dried
by passage over activated alumina. Toluene, pentane and hexane were purified by passage
through BASF R3-11 oxygen scavenger and activated alumina. CDCl CDCl and CHCl CHCl
2
2
2
2
were dried over 4 Å molecular sieves. CD Cl was dried over P O . The following materials
2
2
2
5
were obtained from commercial sources and used without further purification: 4-
methoxybenzenesulfonyl chloride (Aldrich, 99 %), 4-bromoveratrole (Aldrich, 98 %), 5-bromo-
1
,2,3-trimethoxybenzene (Aldrich, 97 %), chlorosulfonic acid (Aldrich, 99 %), 2-methyl-1-
propanol (Aldrich, 99 %), 2-bromoanisole (Aldrich, 97 %), pyridine (Aldrich, 99.8 %),
n
dichloro(diethylamino)phosphine (Alfa aesar, 97 %), BuLi solution (Aldrich, 2.5 M in hexanes),
HCl solution (Aldrich, 2 M in diethyl ether), sodium iodide (Aldrich, > 99 %), lithium iodide
(Aldrich, 99.9 %). The following compounds were prepared by literature procedures: 2-bromo-
4
,5-di-methoxybenzenesulfonyl chloride[12] and (COD)PdMeCl.[13]
NMR spectra were acquired on Bruker DRX-500 or Bruker DRX-400 spectrometers at
1
13
ambient temperature unless otherwise indicated. H and C chemical shifts are reported relative
1
13
31
to SiMe
4
and are internally referenced to residual H and C solvent resonances. P chemical
1
9
shifts are reported relative to externally referenced 85% H
3
PO
4
. F spectra were referenced to
1
9
external BF óEt O, and F chemical shifts are reported relative to CFCl . NMR resonances were
3
2
3
1
31
assigned based on COSY, HMQC, HMBC and H{ P} experiments, as well as trends in
chemical shifts and coupling constants derived from these experiments. Coupling constants are
given in Hz. Mass spectrometry was performed on Agilent 6224 TOF-MS (high resolution) or
Agilent 6130 LCMS (low resolution) instruments.
Gel permeation chromatography (GPC) data were obtained on a Polymer Laboratories PL-
GPC 220 instrument at 150 °C with 1,2,4-trichlorobenzene (stabilized with 125 ppm BHT) as the
12

ACCEPTED MANUSCRIPT
mobile phase. Three PLgel 10 µm Mixed-B LS columns were used. Molecular weights were
calibrated using narrow polystyrene standards (ten-point calibration with M from 570 Da to
n
5
670 kDa) and are corrected for linear polyethylene by universal calibration using the following
-2
3 -1
Mark-Houwink parameters: polystyrene, K = 1.75 ×10 cm g , α = 0.67; polyethylene, K = 5.90
-2
3 -1
×
10 cm g , α = 0.69.[14] DSC measurements were performed on a TA Instruments DSC 2920
instrument. DSC samples (10 mg) were annealed by heating to 170 °C at 20 °C/min, cooled to
4
0 °C at 20 °C/min, and then analyzed while being heated to 170 °C at 20 °C/min.
4
4
.2 Synthesis of Compounds.
i
i
.2.1 3a- Bu. [15] A flask was charged with BuOH (5.0 mL, 54 mmol), pyridine (8.4 mL,
0
.10 mol) and CHCl (50 mL), and cooled to 0 °C. A solution of 4-methoxybenzenesulfonyl
3
chloride (10 g, 50 mmol) in CHCl (30 mL) was added, and the mixture was stirred for 18 h at
3
room temperature. HCl solution (0.1 M in H O, 40 mL) was added, and the mixture was stirred
2
for 5 min and transferred to a separatory funnel. The CHCl layer was separated and washed with
3
H O (3 × 50 mL) and brine (10 mL), and dried over MgSO . The volatiles were removed under
2
4
vacuum to yield a yellow oil. The crude product was purified by silica gel chromatography using
CH
2
Cl
2
as the eluent. The product was isolated as a colorless oil (11 g, 88 %). The ethyl ester of
i
4
-methoxybenzenesulfonate, which is formed by the reaction with EtOH instead of BuOH, was
1
present as a minor impurity. Commercial CHCl contains EtOH as stabilizer. H NMR (CD Cl ):
3
2
2
3
2
3
3
3
δ 7.81 (d, J = 9, 2H, H ), 7.03 (d, J = 9; 2H, H ), 4.05 (q, J = 7, 2H, -SO CH CH ), 3.88
HH
HH
HH
3
2
3
3
3
(
s, 3H, -OCH ), 3.75 (d, J
= 6, 2H, -SO CH CH(CH ) ), 1.91 (sept, J = 7, 1H, -
HH
3
HH
3
2
3 2
3
3
SO CH CH(CH ) ), 1.26 (t, J
= 7, 3H, -SO CH CH ), 0.87 (d, J = 7, 6H, -
HH
3
2
3 2
HH
3
2
3
13
1
4
3
1
SO
3
CH
2
CH(CH
3
)
2
). C{ H} NMR (CD
2
Cl
2
): δ 164.2 (s, C ), 130.4 (s, C ), 127.9 (s, C ), 114.8
2
(
s, C ), 76.6 (s, -SO
3
CH CH(CH ), 67.2 (s, -SO
2
3
)
2
3
CH
2
CH
3
), 56.1 (s, -OCH
3
), 28.4 (s, -
13

ACCEPTED MANUSCRIPT
3 2 3 2 3 2 3 2 3 2 3
SO CH CH(CH ) ), 18.7 (s, -SO CH CH(CH ) ), 14.9 (s, -SO CH CH ). HRMS (APCI/ESI-
+
Mixed mode; m/z): Calcd. for [C H O S+ H] 245.0848, Found: 245.0859.
1
1
16
4
i
i
i
4
.2.2 3b- Bu. 3b- Bu was synthesized analogously to 3a- Bu from 2-bromo-4,5-di-
i
methoxybenzenesulfonyl chloride (9.8 g, 35 mmol), BuOH (3.3 mL, 36 mmol), pyridine (4.8
mL, 60 mmol) and CHCl
3
(70 mL). The product was purified by silica gel chromatography using
1
CH Cl as the eluent, and isolated as a white solid (7.3 g, 60 %). H NMR (CD Cl ): δ 7.53 (s,
2
2
2
2
6
3
8
7
3
9
1
H, H ), 7.20 (s, 1H, H ), 3.91 (s, 3H, H ), 3.89 (s, 3H, H ), 3.80 (d, J = 6, 2H, H ), 1.98 (sept,
HH
3
10
3
11 13
1
JHH = 7, 1H, H ), 0.93 (d, J = 7, 6H, H ). C{ H} NMR (CD Cl ): δ 153.3, 148.1, 127.0,
HH
2
2
1
17.7, 114.4, 112.2, 77.1, 56.5, 56.4, 28.1, 18.5. HRMS (ESI mode; m/z): Calcd. for
+
[
C H BrO S+ Na] 374.9878, Found: 374.9863.
1
2
17
5
i
4
.2.3 3c- Bu. A flask was charged with chlorosulfonic acid (12 mL, 0.18 mol) and cooled to
0
°C. A solution of 5-bromo-1,2,3-trimethoxybenzene (8.0 g, 32 mmol) in CH Cl (40 mL) was
2
2
added and the mixture was stirred for 90 min. The mixture was slowly poured onto ice. After the
ice had thawed, the mixture was transferred to a separatory funnel, and the aqueous layer was
2 2 4
extracted with CH Cl (3 × 40 mL). The organic fractions were combined and dried with MgSO ,
and the volatiles were removed under vacuum to a yield yellow oil. The oil was dissolved in
i
CHCl (60 mL), and a solution of BuOH (4.5 mL, 49 mmol) and pyridine (8.0 mL, 99 mmol) in
3
CHCl (20 mL) was added. The mixture was stirred for 18 h at room temperature. HCl solution
3
(
0.1 M in H O, 80 mL) was added, and the mixture was stirred for 5 min and transferred to a
2
14

ACCEPTED MANUSCRIPT
separatory funnel. The CHCl
3
2
layer was separated and washed with H O (3 × 50 mL) and brine
(
10 mL), and dried over MgSO . The volatiles were removed under vacuum to yield a yellow oil.
4
The crude product was purified by silica gel chromatography using a mixture of 4/1
1
hexanes/ethyl acetate as the eluent. The product was isolated as a yellow oil (3.0 g, 24 %). H
3
9
8
3
10
NMR (CD Cl ): δ 7.08 (s, 1H, H ), 3.94 (s, 3H, H ), 3.92 (s, 3H, H ), 3.87 (d, J = 6, 2H, H ),
2
2
HH
7
3
11
3
12 13
1
3
.84 (s, 3H, H ), 1.98 (sept, J = 7, 1H, H ), 0.93 (d, J = 6, 6H, H ). C{ H} NMR
HH HH
(
CD
2
Cl
2
): δ 157.7, 155.4, 143.3, 122.8, 116.6, 115.1, 77.2, 62.6, 61.1, 56.8, 28.5, 18.8. ESI-MS
+
(
1/1 CH
3
OH/H
2
O; m/z): Calcd. For [2(C13
H
19
O
6
BrS) + Na] 789.0, Found: 789.1.
4
.2.4 P(2-OMe-Ph)
2
Cl.[4a,16] A Schlenk flask was charged with 2-bromoanisole (5.0 mL,
n
4
4
0 mmol) and THF (210 mL), and cooled to -78 °C. BuLi (2.5 M solution in hexanes, 16 mL,
0 mmol) was added via syringe over 15 min. The mixture was stirred at -78 °C for 1 h and a
solution of PCl NEt (3.5 g, 20 mmol) in Et O (30 mL) was added. The mixture was stirred at
2
2
2
room temperature for 18 h to yield a clear yellow solution. The volatiles were removed under
vacuum. The resulting yellow solid was taken up in Et O (100 mL) and washed with H O (100
2
2
mL). The aqueous layer was extracted with Et O (3 × 75 mL). The combined organic fractions
2
were washed with brine (20 mL) and dried over MgSO
vacuum to afford P(2-OMe-Ph) NEt as a yellow solid (5.7 g, 87 %). A Schlenk flask was
charged with P(2-OMe-Ph) NEt (3.1 g, 10 mmol) and THF (50 mL), and cooled to -78 °C. HCl
4
, and the volatiles were removed under
2
2
2
2
solution (2.0 M solution in diethyl ether, 10 mL, 20 mmol) was added via syringe to form a
white cloudy solution. The mixture was stirred at -78 °C for 1 h and filtered, and the volatiles
were removed from the filtrate under vacuum to yield a white solid (2.5 g, 89 %). The typical
15

ACCEPTED MANUSCRIPT
3
1
1
purity was ca. 93% as determined by P{ H} NMR. The product was used without further
3
1
1
1
3
purification. P{ H} NMR (CD Cl ): δ 69.6. H NMR (CD Cl ): δ 7.43 (t, J = 8, 2H), 7.36-
2
2
2
2
HH
3
3
3
7
.34 (m, 2H), 7.00 (t, J = 8, 2H), 6.93 (dd, J = 8, J = 5, 2H), 3.82 (s, 6H).
HH HH PH
i
i
4
.2.5 1a- Bu. A Schlenk flask was charged with 3a- Bu (1.2 g, 5.0 mmol) and THF (38 mL),
n
and cooled to -78 °C. BuLi (2.5 M solution in hexanes, 2.0 mL, 5.0 mmol) was added via
syringe over 5 min. The mixture was stirred at -78 °C for 1 h and a solution of P(2-OMe-Ph) Cl
2
(
1.4 g, 5.0 mmol) in THF (10 mL) was added. The mixture was stirred at room temperature for
8 h to yield a clear yellow solution. The volatiles were removed under vacuum. The resulting
yellow oil was taken up in H O (50 mL) and extracted with CH Cl (3 × 50 mL). The combined
1
2
2
2
organic fractions were washed with brine (20 mL) and dried over MgSO , and the volatiles were
4
removed under vacuum to yield a yellow solid. The crude product was purified by silica gel
chromatography, using a 4/1 hexanes/ethyl acetate mixture as the eluent. The product was
3
1
1
1
isolated as a white solid (0.720 g, 30%). P{ H} NMR (CD Cl ): δ -28.1. H NMR (CD Cl ): δ
2
2
2
2
3
4
3
3
10
3
4
8
.06 (dd, J = 8, J = 4, 1H, H ), 7.36 (t, J = 8; 2H, H ), 6.96 (dd, J = 8, J = 3, 1H,
HH
PH
HH
HH
HH
4
3
4
9
3
11
6
12
H ), 6.92 (dd, JHH = 8, JPH = 5, 2H, H ), 6.85 (t, JHH = 8, 2H, H ), 6.57 (m, 3H, H and H ),
3
15
14
13
3
16
3
0
.79 (d, JHH = 6, 2H, H ), 3.72 (s, 6H, H ), 3.64 (s, 3H, H ), 1.85 (sept, JHH = 7, 1H, H ),
3
17 13
1
3
5
2
.88 (d, J = 7, 6H, H ). C{ H} NMR (CD Cl ): δ 163.1 (d, J = 1, C ), 161.5 (d, J = 17,
HH
2
2
PC
PC
8
1
1
12
3
3
2
2
C ), 141.6 (d, J = 33, C ), 134.2 (s, C ), 133.1 (d, J = 4, C ), 132.7 (d, J = 26, C ), 130.8
PC
PC
PC
1
0
1
7
2
6
11
4
3
(
s, C ), 125.1 (d, J =16, C ), 122.6 (d, J = 1, C ), 121.4 (s, C ), 113.3 (s, C ), 110.8 (d, J
PC
PC
PC
9
5
15
4
14
13
16
17
=
1, C ), 76.7 (d, J = 3, C ), 56.0 (d, J = 1, C ), 55.7 (s, C ), 28.4 (s, C ), 18.9 (s, C ).
PC
PC
+
HRMS (APCI/ESI-Mixed mode; m/z): Calcd. for [C H O PS + H] 489.1501, Found: 489.1495.
2
5
29
6
16

ACCEPTED MANUSCRIPT
i
i
i
i
4
.2.6 1b- Bu. 1b- Bu was synthesized analogously to 1a- Bu from 3b- Bu (0.71 g, 2.0 mmol)
and P(2-OMe-Ph) Cl (0.56 g, 2.0 mmol). The volatiles were removed under vacuum, and the
2
resulting yellow oil was taken up in H O (20 mL) and extracted with ethyl acetate (3 × 20 mL).
2
The combined organic fractions were washed with brine (5 mL) and dried over MgSO , and the
4
volatiles were removed under vacuum to yield a yellow solid. The crude product was purified by
silica gel chromatography using a 3/1 hexanes/ethyl acetate mixture as the eluent. The product
3
1
1
1
2 2
was isolated as a white solid (0.450 g, 43 %). P{ H} NMR (CD Cl ): δ -27.6. H NMR
4
3
3
10
3
4
(
2 2
CD Cl ): δ 7.59 (d, JPH = 3, 1H, H ), 7.35 (t, JHH = 8, 2H, H ), 6.91 (dd, JHH = 8, JPH = 5, 2H,
9
3
11
12
3
6
13
H ), 6.85 (t, JHH = 8, 2H, H ), 6.60 (br, 2H, H ), 6.50 (d, JPH = 2, 1H, H ), 3.92 (s, 3H, H ),
3
16
15
14
3
17
3
0
1
.84 (d, J = 6, 2H, H ), 3.72 (s, 6H, H ), 3.41 (s, 3H, H ), 1.86 (sept, J = 7, 1H, H ),
HH
HH
3
18 13
1
2
8
5
.89 (d, J = 6, 6H, H ). C{ H} NMR (CD Cl ): δ 161.4 (d, J = 17, C ), 152.5 (s, C ),
HH
2
2
PC
4
12
2
2
1
1
10
49.3 (s, C ), 134.0 (s, C ), 133.2 (d, J = 28, C ), 131.5 (d, J = 31, C ), 130.7 (s, C ),
PC
PC
1
7
11
6
3
3
9
1
25.7 (d, J =17, C ), 121.4 (s, C ), 118.4 (s, C ), 113.7 (d, J = 5, C ), 110.7 (s, C ), 76.8 (d,
PC
PC
5
16
13
15
14
17
18
J
PC = 4, C ), 56.5 (s, C ), 56.0 (s, C ), 55.8 (s, C ), 28.4 (s, C ), 18.9 (s, C ). HRMS
+
(APCI/ESI-Mixed mode; m/z): Calcd. for [C26
H O
31 7
PS + H] 519.1606, Found: 519.1616.
17

ACCEPTED MANUSCRIPT
i
i
i
i
4
.2.7 1c- Bu. 1c- Bu was synthesized analogously to 1a- Bu from 3c- Bu (1.2 g, 3.0 mmol)
and P(2-OMe-Ph) Cl (0.85 g, 3.0 mmol). The volatiles were removed under vacuum, and the
2
resulting yellow oil was taken up in H O (50 mL) and extracted with ethyl acetate (3 × 50 mL).
2
The combined organic fractions were washed with brine (10 mL) and dried over MgSO , and the
4
volatiles were removed under vacuum to yield a yellow solid. The crude product was purified by
silica gel chromatography using a 5/1 hexanes/ethyl acetate mixture as the eluent. The product
3
1
1
1
was isolated as a white solid (0.800 g, 49 %).
P{ H} NMR (CD
2
Cl
2
): δ -21.9. H NMR
3
10
3
4
9
3
(
CD
2
Cl
2
): δ 7.36 (t, JHH = 8, 2H, H ), 6.93 (dd, JHH = 8, JPH = 5, 2H, H ), 6.87 (t, JHH = 8, 2H,
1
1
12
6
13
14
16
H ), 6.70 (br, 2H, H ), 6.32 (s, 1H, H ), 3.99 (s, 3H, H ), 3.86 (s, 3H, H ), 3.75 (s, 6H, H ),
3
17
15
3
18
3
3
.72 (d, J = 6, 2H, H ), 3.38 (s, 3H, H ), 1.89 (sept, J = 7, 1H, H ), 0.86 (d, J = 7, 6H,
HH
HH
HH
1
9
13
1
2
8
5
3
3
H ). C{ H} NMR (CD Cl ): δ 161.7 (d, J = 17, C ), 156.8 (s, C ), 154.4 (d, J = 4, C ),
2
2
PC
PC
4
1
1
12
10
2
2
1
1
43.1 (s, C ), 136.4 (d, J = 37, C ), 134.5 (s, C ), 130.8 (s, C ), 126.6 (d, J = 21, C ),
PC PC
1
7
11
6
9
5
17
26.5 (d, J =19, C ), 121.5 (s, C ), 113.9 (s, C ), 110.8 (s, C ), 76.7 (d, J = 2, C ), 62.1 (s,
PC
PC
13
14
16
15
18
19
C ), 60.9 (s, C ), 56.1 (s, C ), 55.7 (s, C ), 28.5 (s, C ), 18.8 (s, C ). HRMS (ESI mode; m/z):
+
Calcd. for [C27
H
33
O
8
PS + H] 549.1712, Found: 549.1710.
18

ACCEPTED MANUSCRIPT
i
4
.2.8 Na[1a]. A flask was charged with 1a- Bu (0.72 g, 1.5 mmol), NaI (0.64 g, 4.0 mmol)
and CH CN (20 mL). CH Cl (15 mL) was added to afford a clear solution. The mixture was
3
2
2
stirred at room temperature for 2 d to afford a white suspension, which was filtered to afford
3
1
1
Na[1a] as a white powder. The product was dried under vacuum for 18 h (0.39 g, 57 %). P{ H}
1
3
4
3
3
NMR (CD OD): δ -28.4. H NMR (CD OD): δ 8.02 (dd, J = 8, J = 4, 1H, H ), 7.30 (t, J
HH
3
3
HH
PH
10
3
4
9
3
4
4
=
8; 2H, H ), 6.93 (dd, J = 8, J =5, 2H, H ), 6.91 (dd, J = 9, J = 3, 1H, H ), 6.80 (t,
HH
PH
HH
HH
3
11
12
3
4
6
14
J
HH = 8, 2H, H ), 6.60 (br, 2H, H ), 6.47 (t, JPH = JHH = 3, 1H, H ), 3.69 (s, 6H, H ), 3.56 (s,
1
3
13
1
2
8
5
1
3
3
H, H ). C{ H} NMR (CD OD): δ 162.4 (d, JPC = 16, C ), 161.8 (s, C ), 143.2 (d, JPC = 27,
1
2
2
12
10
3
3
1
C ), 138.2 (d, JPC = 23, C ), 134.8 (s, C ), 131.1 (s, C ), 130.5 (d, JPC = 5, C ), 127.0 (d, JPC
7
6
11
4
9
14
13
=
14, C ), 122.3 (s, C ), 121.9 (s, C ), 113.8 (s, C ), 111.5 (s, C ), 56.0 (s, C ), 55.5 (s, C ).
-
HRMS (ESI mode; m/z): Calcd. for [C H NaO PS + Cl] 489.0304, Found: 489.0325.
2
1
20
6
i
4
.2.9 Na[1b]. Na[1b] was synthesized analogously to Na[1a] from 1b- Bu (0.36 g, 0.70
mmol), NaI (0.450 g, 3.0 mmol) and CH CN (5 mL). The mixture was stirred at room
3
temperature for 2 d to afford a white suspension, which was filtered to afford Na[1b] as a white
3
1
1
powder. The product was dried under vacuum for 18 h (0.29 g, 85 %). P{ H} NMR (CD OD):
3
1
4
3
3
10
δ -27.7. H NMR (CD OD): δ 7.68 (d, J = 4, 1H, H ), 7.29 (t, J = 8, 2H, H ), 6.93 (dd,
3
PH
HH
3
4
9
3
11
12
3
JHH = 8, J = 4, 2H, H ), 6.81 (t, J = 8, 2H, H ), 6.64 (br, 2H, H ), 6.46 (d, J = 2, 1H,
PH
HH
PH
6
13
15
14 13
1
H ), 3.89 (s, 3H, H ), 3.69 (s, 6H, H ), 3.36 (s, 3H, H ). C{ H} NMR (CD
3
OD): δ 162.5 (d,
2
8
5
4
2
2
12
10
J
PC = 16, C ), 150.9 (s, C ), 149.9 (s, C ), 144.5 (d, JPC = 29, C ), 134.8 (s, C ), 130.9 (s, C ),
1
7
1
1
11
6
3
1
28.1 (d, J =11, C ), 128.0 (d, J = 23, C ), 121.8 (s, C ), 119.2 (s, C ), 112.6 (s, C ), 111.4
PC PC
19

ACCEPTED MANUSCRIPT
9
13
15
14
(
s, C ), 56.4 (s, C ), 56.0 (s, C ), 55.9 (s, C ). HRMS (ESI mode; m/z): Calcd. for
-
[
C H NaO PS + Cl] 519.0410, Found: 519.0430.
2
2
22
7
i
4
.2.10 Li[1c]. A vial was charged with 1c- Bu (0.31 g, 0.60 mmol), LiI (0.35 g, 2.6 mmol)
and CH CN (10 mL), and covered with aluminum foil. The mixture was stirred at room
3
temperature for 4 d. The volatiles were removed under vacuum. THF was added to afford a white
suspension, which was filtered to afford Li[1c] as a white powder. The product was dried under
31
1
1
3 3
vacuum for 18 h (0.14 g, 52 %). P{ H} NMR (CD OD): δ -22.7. H NMR (CD OD): δ 7.29 (t,
3
10
3
4
9
3
11
J
HH = 8, 2H, H ), 6.93 (dd, JHH = 8, JPH = 5, 2H, H ), 6.82 (t, JHH = 7, 2H, H ), 6.68 (br, 2H,
1
2
3
6
13
14
16
H ), 6.27 (d, J = 2, 1H, H ), 3.97 (s, 3H, H ), 3.84 (s, 3H, H ), 3.70 (s, 6H, H ), 3.32 (s, 3H,
PH
1
5
+
H ). ESI-MS (1/1 CH OH/H O; m/z): Calcd. for [C H O PS + 2H] 493.1, Found: 493.2;
3
2
23 24
8
-
Calcd. for [C H O PS] 491.1, Found: 491.3.
2
3
24
8
4
.2.11 2a. A vial was charged with Na[1a] (0.14 g, 0.30 mmol), (COD)PdMeCl (80 mg,
0
.30 mmol) and CH Cl (6 mL), and the mixture was stirred at room temperature for 1h to afford
2
2
a cloudy yellow solution. Pyridine (24 µL, 0.30 mmol) was added, and the mixture was stirred
for 18 h, filtered through a Celite pipette, layered with pentane and cooled to -40 °C. After 1 d,
20

ACCEPTED MANUSCRIPT
colorless X-ray quality crystals formed. The crystals were collected by filtration and dried under
3
1
1
1
vacuum for 18 h (0.11 g, 59 %). P{ H} NMR (CD Cl ): δ 21.8. H NMR (CD Cl ): δ 8.76 (dd,
2
2
2
2
3
4
13
3
4
3
3
4
JHH = 5, J = 2, 2H, H ), 8.01 (dd, J = 9, J = 6, 1H, H ), 7.88 (tt, J = 8, J = 1, 1H,
HH
HH
PH
HH
HH
1
5
3
10
3
14
10
H ), 7.54 (t, J = 8, 2H, H ), 7.48 (t, J = 7, 2H, H ), 7.56-7.46 (br, overlap with H and
HH
HH
1
4
12
3
11
3
4
9
3
H , 2H, H ), 7.03 (t, J = 8, 2H, H ), 6.99 (dd, J = 8, J =5, 2H, H ), 6.95 (dd, J = 8,
HH
HH
PH
HH
4
4
3
4
6
17
16
JHH = 2, 1H, H ), 6.78 (dd, J = 12, J = 3, 1H, H ), 3.71 (s, 6H, H ), 3.67 (s, 3H, H ),
PH
HH
3
13
1
2
8
3
0
.26 (d, JPH = 3, 3H, Pd-CH
3
). C{ H} NMR (CD
2
Cl
2
): δ 161.0 (d, JPC = 3, C ), 159.8 (d, JPC
5
13
2
2
15
12
10
=
9, C ), 150.7 (s, C ), 141.6 (d, JPC = 15, C ), 138.7 (s, C ), 137.8 (br, C ), 133.6 (s, C ),
3
3
1
1
4
14
2
6
1
1
29.8 (d, JPC = 9, C ), 129.6 (d, JPC = 48, C ), 125.5 (d, JPC =2, C ), 121.3 (d, JPC = 3, C ),
3
11
1
7
4
3
9
20.9 (d, J = 12, C ), 116.5 (d, J =56, C ), 114.2 (s, C ), 111.8 (d, J = 5, C ), 55.8 (s,
PC
PC
PC
17
16
2
12
12
C ), 55.7 (s, C ), 0.3 (d, J = 4, Pd-CH ). The H and C resonance are broad because the
PC
3
rate of anisyl group exchange is not in the fast exchange limit. HRMS (ESI mode; m/z): Calcd.
+
for [C H NO PPdS + H] 632.0488, Found: 632.0492.
2
7
28
6
4
.2.12 2b. Route 1. 2b was synthesized analogously to 2a from Na[1b] (0.15 g, 0.30 mmol),
COD)PdMeCl (80 mg, 0.30 mmol), pyridine (25 µL, 0.30 mmol) and CH Cl (5 mL). The
CH Cl solution was layered with pentane and cooled to -40 °C. After 1 d, colorless X-ray
quality crystals formed. The crystals were collected by filtration and dried under vacuum for 18 h
(
2
2
2
2
3
1
1
1
3
4
(
0.17 g, 86 %). P{ H} NMR (CD Cl ): δ 21.0. H NMR (CD Cl ): δ 8.76 (dd, J = 5, J
=
HH
2
2
2
2
HH
1
3
3
4
15
4
3
3
2
, 2H, H ), 7.88 (tt, J = 8, J = 2, 1H, H ), 7.61 (d, J = 4, 1H, H ), 7.54 (t, J = 8, 2H,
HH
HH
PH
HH
21

ACCEPTED MANUSCRIPT
1
0
3
14
3
10
14
12
H ), 7.48 (t, JHH = 7, 2H, H ), 7.62-7.46 (br, overlap with H , H and H , 2H, H ), 7.03 (t,
3
11
3
4
9
3
6
JHH = 8, 2H, H ), 6.99 (dd, J = 8, J =5, 2H, H ), 6.68 (d, J = 11, 1H, H ), 3.90 (s, 3H,
HH
PH
PH
1
6
18
17
3
13
1
H ), 3.71 (s, 6H, H ), 3.50 (s, 3H, H ), 0.29 (d, J = 3, 3H, Pd-CH3). C{ H} NMR
PH
2
8
13
4
3
5
(
CD Cl ): δ 161.0 (d, J = 3, C ), 150.8 (s, C ), 150.5 (s, C ), 149.0 (d, J = 8, C ), 143.3 (d,
2 2 PC PC
2
2
15
12
10
14
3
JPC = 16, C ), 138.6 (s, C ), 137.5 (br, C ), 133.5 (s, C ), 125.5 (s, C ), 120.9 (d, J = 11,
PC
11
1
1
2
6
1
7
3
C ), 118.9 (d, J = 53, C ), 117.6 (d, J = 4, C ), 117.0 (d, J =57, C ), 111.7 (d, J = 5,
PC
PC
PC
PC
3
3
9
16
17
18
2
C ), 111.6 (d, JPC = 12, C ), 56.4 (s, C ), 56.0 (s, C ), 55.8 (s, C ), 0.3 (d, JPC = 4, Pd-CH
3
).
1
2
12
The H and C resonance are broad because the rate of anisyl group exchange is not in the fast
+
7
exchange limit. HRMS (APCI/ESI-Mixed mode; m/z): Calcd. for [C28H30NO PPdS + H]
i
6
62.0594, Found: 662.0609. Route 2. A vial was charged with 1b- Bu (52 mg, 0.10 mmol),
(
COD)PdMeCl (26 mg, 0.10 mmol) and CH Cl (3 mL), and the mixture was stirred at room
2 2
temperature for 1h to afford a clear yellow solution. Pyridine (8.1 µL, 0.10 mmol) was added,
and the mixture was stirred for 18 h, filtered through Celite, layered with pentane, and cooled to -
4
0 °C. After 1 d, colorless X-ray quality crystals formed. The crystals were collected by filtration
and dried under vacuum for 18 h (34 mg, 51 %).
i
4
.2.13 Generation of 2c. A J-Young valved NMR tube was charged with 1c- Bu (11 mg,
0
.020 mmol) and (COD)PdMeCl (10 mg, 0.037 mmol), and CD
2
Cl
2
was added by vacuum
3
1
1
transfer. The mixture was thawed and formed a clear yellow solution. P{ H} NMR (CD Cl ): δ
2
2
1
3
2
5.0. H NMR (CD Cl ) Pd-Me region: δ 0.81 (d, J = 3Hz). After 18 h, pyridine (1.6 µL, 0.020
2 2 PH
mmol) was added, and the reaction was monitored by NMR and found to be complete after 3 d.
22

ACCEPTED MANUSCRIPT
3
1
1
1
3
P{ H} NMR (CD
2
Cl
2
): δ 20.1. H NMR (CD
2
Cl
2
) Pd-Me region: δ 0.46 (d, JPH = 2 Hz). These
data indicate that 2c was successfully generated by this route. However, attempted isolation of 2c
was unsuccessful due to decomposition.
4
4
.3 Polymerization Procedures.
.3.1 Ethylene Homopolymerization. Polymerization reactions were performed in a Parr
3
00 mL stainless steel autoclave, which was equipped with a mechanical stirrer, thermocouple
and water cooling loop and controlled by a Parr 4842 controller. In a glovebox, a 200 mL glass
autoclave liner was charged with solution of the catalyst in chlorobenzene (1 mL), and toluene
(49 mL) was then added. For catalyst loadings larger than 5 µmol, the catalyst was weighed
directly into the glass liner and 50 mL of solvent was added. The glass liner was placed in a
stainless steel autoclave, which was sealed and removed from the glovebox. The autoclave was
heated to the target temperature and pressurized with ethylene while the contents were stirred.
After 2 h, the autoclave was cooled to 25 °C and vented. Acetone (50 mL) was added to
precipitate the polymer. The polymer was collected by filtration, rinsed with acetone, and dried
under vacuum.
4
.3.2 Ethylene/VF Copolymerization. In a glove box, an injection cylinder was charged
with a solution of the catalyst (10 µmol) in chlorobenzene (10 mL) and connected to the
autoclave. Toluene (40 mL) was added to glass autoclave liner. The liner was placed in the
autoclave, and the autoclave was sealed and removed from the glove box. The autoclave was
pressurized with VF to the desired pressure and ethylene was added until the total pressure
reached 300 psi, while the mixture was stirred (100 rpm). The reactor was heated to the 80 °C
and the catalyst solution was injected from the injection cylinder by 450 psi of N
2
. The stirring
rate was increased to 170 rpm after the temperature stabilized at 80 °C. After 2 h, the autoclave
23

ACCEPTED MANUSCRIPT
was cooled to 25 °C and vented. Acetone (50 mL) was added to precipitate the polymer. The
polymer was collected by filtration, rinsed with acetone, and dried under vacuum.
Acknowledgements. The authors thank Drs. Antoni Jurkiewicz, Chang-Jin Qin and Alexander
Filatov for assistance with NMR spectroscopy, mass spectrometry and X-ray crystallography
respectively. This work was supported by National Science Foundation grant CHE-1709159.
Supplementary data
The supplementary data contain crystallographic data for 2a,b and NMR spectra of all
compounds and are available on the publisher's website.
Accession Codes CCDC 1913932 and 1850727 contain the supplementary crystallographic data
(CIF files) for this paper. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by
contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: +44 1223 336033.
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Graphical Abstract
Graphical Abstract Synopsis (50 word)
The phosphine-arenesulfonate ligands Na[1a,b] and Li[1c] react with (COD)PdMeCl and
pyridine to generate (PO)PdMe(pyridine) complexes 2a-c, which contain 1-3 methoxy groups on
the benzo linker. 2a,b have been characterized by X-ray crystallography while 2c is thermally
unstable. The ethylene polymerization and ethylene/vinyl-fluoride copolymerization behavior of
2
a,b have been investigated.
Highlights
•
•
•
•
Phosphine-arenesulfonate ligands with OMe-substituted benzo linkers were prepared
The corresponding (PO)PdMe(py) complexes were prepared and characterized
These (PO)PdMe(py) complexes polymerize ethylene to linear polyethylene
These (PO)PdMe(py) complexes copolymerize ethylene and vinyl fluoride
28

ACCEPTED MANUSCRIPT
Highlights
•
•
•
•
Phosphine-arenesulfonate ligands with OMe-substituted benzo linkers were prepared
The corresponding (PO)PdMe(py) complexes were prepared and characterized
These (PO)PdMe(py) complexes polymerize ethylene to linear polyethylene
These (PO)PdMe(py) complexes copolymerize ethylene and vinyl fluoride