配位・挿入機構による極性モノマー/エチレンの直鎖コポリマー合成配位子の設計と分子量への影響（M1岩本紘明君） 有機元素化学研究室の雑誌会は30分プレゼン+全員からの質問、ディスカッションで実施しています。30分という限られた時間で「わかりやすく説明する」ことが要求されます。

1. 配位・挿⼊入機構による
極性モノマー/エチレンの直鎖コポリマー合成
配位⼦子の設計と分⼦子量量への影響
2014, 12, 9
後期雑誌会
岩本 紘明

2. ポリエチレンの種類
1953, Ziegler-‐‑‒Natta Catalyst
■ 低密度度ポリエチレン (LDPE)
密度度: 0.910–0.940 g/cm3
合成法: ラジカル重合
性質: 柔らかい, 透明
構造: 分岐型
■ ⾼高密度度ポリエチレン (HDPE)
密度度: >0.942 g/cm3
合成法: ⾦金金属触媒重合
性質: ⾼高強度度, 結晶性
構造: 直鎖
1933, Imperial Chemical Industries (ICI)
n
O2 (radical initiator)
10–20 MPa
Karl
Ziegler Guilio
Natta
n
TiCl4, Et3Al
2

3. 狭い分⼦子量量分散度度 (ca. 2)
タクチシティーの制御 (アイソタクチック or シンジオタクチック )
⾦金金属触媒によるポリオレフィン重合の発達
■ 不不均⼀一系 触媒 (Multi-‐‑‒Site Type): Zieglar-‐‑‒Natta Catalyst
■ 均⼀一系 触媒 (Single-‐‑‒Site Type): Metallocene catalyst
問題点: 分⼦子量量分散度度 (ca.4),
微⼩小構造のコントロール
Ti Ti
Ti
Zr
Cl
Cl
Cp2ZrCl
Kaminsky
Catalyst
Sinn, H; Kaminsky, W; Vollmer, H. -J.; Woldt, E. Angew. Chem. Int. Ed. 1980, 19, 390.
Walter Kaminsky
年年間５百万トンのLLDPE(Linear Low Density Polyethylene)が
Single-‐‑‒Site 触媒で製造されている
Baier, M. C.; Zuideveld, M. A.; Mecking, S. Angew. Chem. Int. Ed. 2014, 53, 9722.
Multi-‐‑‒site
Cp2ZrCl, MAO
3

4. ⾦金金属触媒による配位­−挿⼊入重合の⼀一般的な重合機構
L
L
M
P
H
L
L
M
P
H
L
L
M
P
L
L
M
H
L
L
M
P H
L
L
M
P H
P
直鎖ポリマー オリゴマー 分岐ポリマー
propagation chain transfer
β-‐‑‒hydride
elimination chain walking
branch formation
Nakamura. A.; Ito, S.; Nozaki, K. Chem. Rev. 2009, 109, 5215.
4

5. コポリマーの種類
グラフトコポリマー
ブロックコポリマー
末端修飾型ポリオレフィン
局在型 分散型
■ 機能性官能基をポリマーへと導⼊入することで機能性の発現
特性: 粘着⼒力力, 染⾊色性, 印刷適性, 適合性
分岐型コポリマー (低密度度)
合成:ラジカル共重合
直鎖コポリマー (⾼高密度度)
合成: 今回のテーマ
Nakamura. A.; Ito, S.; Nozaki, K. Chem. Rev. 2009, 109, 5215.
5

6. 極性モノマーとエチレンの直鎖コポリマー
Post-‐‑‒functionalization
1) ROMP
2) Hydrogenaion
1) ADMET
2) Hydrogenaion
過酷な反応条件
特異異なモノマー
&
多段階合成
直接的なアプローチ
Copolymerization
n
FG
FG
n n
+ FG
FG
yx n
極性モノマーの効果により材料料表⾯面の性質を変える
FG
yx n
直鎖コポリマー ⾼高密度度ポリエチレンの応⽤用範囲の拡⼤大
Nakamura. A.; Ito, S.; Nozaki, K. Chem. Rev. 2009, 109, 5215.
6

7. 直鎖コポリマー合成における障害
■ 従来の前期遷移⾦金金属触媒による合成
+ FG
FG
mn
Early Transition Metal
Catalyst(Zr, Ti, etc.)
■ よりオレフィンと親和性の⾼高い後期遷移⾦金金属触媒による合成
酸素原⼦子などを含む極性ビニルモノマーは触媒を失活させてしまう
L
L
M
R
H
L
L
M
R
H
β-‐‑‒Hydride Elimination
β-‐‑‒⽔水素脱離離の競合により⾼高分⼦子量量体を得ることが困難
配位⼦子の効果による成⻑⾧長反応のコントロールへ
L=ligand
M＝Ni or Pd
Nakamura. A.; Ito, S.; Nozaki, K. Chem. Rev. 2009, 109, 5215.
Oligomer
L
L
M
R
Polymer
propagation
Chain Transfer
7

8. 後期遷移⾦金金属触媒によるポリマー合成
■ αジイミン配位⼦子を⽤用いた⾼高分⼦子量量体重合の達成
Brookhart Catalyst
N N
Ni
Br Br
Maurice S. Brookhart
問題点： β⽔水素脱離離を抑制できていないので分岐型ポリマーが⽣生成する
Chain Walking
嵩⾼高い配位⼦子により連鎖移動反応を抑制 → ⾼高分⼦子量量体（>105
g/mol)
N
N
Ni
P
H
N
N
Ni
P
H
N
N
Ni
P H
N
N
Ni
H
P
N
N
Ni
P
N
N
Ni
P H
propagation
Chain Transfer
Ittel. S. D.; Johnson, L. K.; Brookhart, M. Chem. Rev. 2000, 100, 1169.
Johnson, K. L.; Brookhart, M. et al. J. Am. Chem. Soc. 1995, 117, 6414.
n
Ni Catalyst / MAO
(0.83×10-6 mol)
toluene, 25 ºC, 30 min
1 atm
Mn = 190×103 g/mol
Mw / Mn = 2.2
branches / 1000C = 71
Tm = 39 ºC
8

9. ホスフィンースルホン酸配位⼦子の登場
Drent, E.; van Dijk, R.; van Ginkel, R. van Oort, B.; Pugh, R. I. Chem. Commun. 2002, 744.
異異なる元素が⾦金金属上に配位した⾮非対称⼆二座配位⼦子が直鎖の合成に有利利なのでは？
1987年年、Union CarbideのMurrayがホスフィンースルホン酸配位⼦子を⽤用いた
エチレンのオリゴマー化を報告
1964年年、SHOP (Shell Higher Olefin Process) の開発
酸素とリンがNiに配位する
触媒を⽤用いた直鎖C4–C8脂肪族
αオレフィンの⼯工業的⽣生産
Keim, W. Angew. Chem. Int. Ed. 2013, 52, 12492.
P
O
Ni
Ph
Ph
Ph3P
Ph
Ph
年年間200,000トン
2002年年、ShellのDrentらアクリル酸メチルを⽤用いた直鎖コポリマー合成を報告
O
O+
Pd(OAc)2 (0.1 mmol)
ligand (0.12 mmol)
toluene (25 ml)
80 ºC, 15 h25 ml30 bar Mn = 12.8×103 g/mol
Mw / Mn = 1.6
CO2Me
yx n
P
S OHO
O
R1 R1
R1 = 2-MeO-C6H4
9

10. ⾮非対称⼆二座配位⼦子はcis-‐‑‒体とtrans-‐‑‒体が存在する
■ X線構造解析による⽴立立体構造の決定
cis trans
P
S OO
O
Pd
Me
N
R1 R1
P
S OO
O
Pd
Me
R1 R1
N
MeO
R1 =
cis-‐‑‒体のみ単離離 X-ray structure of cis-complex
R1 = 3.80%, R2 = 8.86%, GOF = 1.106
cis trans
P
S OO
O
Pd
Me
N
Me Me
P
S OO
O
Pd
Me
Me Me
N
■ 計算による解析
0 Kcal/mol +10.7 Kcal/mol
TS
+20.6 Kcal/mol
B3LYP/ 6-31G* and Lanl2dz
Noda, S.; Nakamura, A.; Kochi, T.; Chung, L. W.; Morokuma, K.; Nozaki, K. J. Am. Chem. Soc. 2009, 131, 14088.
trans-‐‑‒体の⽅方が不不安定
異異性化には⼤大きな
エネルギーが必要
アルキル配位⼦子の強いトランス影響によりcis-‐‑‒体が安定化する
10

11. +17.0
TS
+23.7
TS +27.7
–1.2
–10.6
P
O
Pd
P
O
Pd
H
P
O
Pd
Py
P
O
Pd
+7.6
ポリエチレン成⻑⾧長反応の各段階のエネルギー計算
0.0
TS
+17.5
TS +38.9
+8.7
B3LYP/ 6-‐‑‒31G* and Lanl2dz
Noda, S.; Nakamura, A.; Kochi, T.; Chung, L. W.; Morokuma, K.; Nozaki, K. J. Am. Chem. Soc. 2009, 131, 14088.
P
O
P
S OO
O
Me Me
=
P
O
Pd
Py
P
O
Pd
P
O
Pd
P
O
Pd
H
ΔG [kcal/mol]
cis-‐‑‒trans異異性化の経路路
11

12. βヒドリド脱離離のエネルギー計算
B3LYP/ 6-‐‑‒31G* and Lanl2dz
Noda, S.; Nakamura, A.; Kochi, T.; Chung, L. W.; Morokuma, K.; Nozaki, K. J. Am. Chem. Soc. 2009, 131, 14088.
P
O
Pd
Py
0.0
+10.7
TS
+27.4
+19.6
TS
+19.9
+9.4
ΔG [kcal/mol]
P
O
Pd
Py
TS
+20.６
TS
+20.4
P
O
Pd
H
+18.6
P
O
Pd
H
P
O
Pd
Hcis-‐‑‒trans異異性化の遷移状態
ピリジンの脱離離の遷移状態
のエネルギー準位が⾼高い
← 異異性化において中間体の存在が⽰示唆される
12

13. cis-‐‑‒trans異異性化の経路路
B3LYP/ 6-‐‑‒31G* and Lanl2dz
Noda, S.; Nakamura, A.; Kochi, T.; Chung, L. W.; Morokuma, K.; Nozaki, K. J. Am. Chem. Soc. 2009, 131, 14088.
cis-‐‑‒
0.0 kcal/mol
intermediate
18.6 kcal/mol
スルホン酸のもう⼀一つの酸素を使った擬似回転(Pseudorotation)の様な機構
Pd
OS
O
P
O
Py
Pd
PyO
OS
O
P
Pd
OS
O
P
O
Py
Pd
OS
O
P
O
Py
TS
31 kcal/mol
trams-‐‑‒
10.7 kcal/mol
TS
+20.６ kcal/mol
TS
+20.4 kcal/mol
Zhou, X.;Lau, K.-C..;Petro, B. J.; Jordan, R. F. Organometallics. 2014, ASAP.
L2 L5
L1
L3
M
L4
13
L1 L3
L3
L2
M
L5

14. 様々な極性ビニルモノマーとエチレンの共重合を達成
CN
yx n
CN+
2.5 ml4.0 MPa
Mn = 12.3×103
Mw / Mn = 1.6
i.r. = 2.0%, Tm = 121.4
Pd catalyst (0.01 mmol)
toluene (25 ml)
80 ºC, 270 h
P
S OO
O
Pd
Me
N
R1 R1
Kochi, T.; Noda, S.; Yoshimura. K.; Nozaki, K. J. Am. Chem. Soc. 2007, 129, 8948.
F+
0.28 MPa1.4 MPa
Pd catalyst (0.01 mmol)
toluene (50 ml)
80 ºC, 270 h F
yx n
Mn = 14.5×103
Mw / Mn = 3.0
Tm = 132.6 ºC
P
S OO
O
Pd
Me
N
R1 R1
R1 = 2-MeO-C6H4
R1 = 2-MeO-C6H4
Weng, W.; Shen, Z.; Jordan. R. F. J. Am. Chem. Soc. 2007, 129, 15450.
■ アクリロニトリルとの共重合
■ フッ化ビニルとの共重合
■ その他多くの共重合が報告されている
OEt
yx n
Mn = 4.8×103
Mw / Mn = 2.0
i.r. = 2.0%
OO O
n
Mn = 8.0×103
Mw / Mn = 1.7
x y
Jordan, R. F. et al. J. Am. Chem. Soc. 2007, 129, 8946.
Claverie, J. P. et al. Macromolecules. 2008, 41, 2309.
yx n
Mn = 6.5×103
Mw / Mn = 2.4
i.r. = 4.9%
O
Sen, A. et al. Organometallics. 2008, 27, 3331.
14

15. ホスフィン­−スルホン酸配位⼦子の問題点
ポリエチレン系プラスチックの実⽤用的な平均分⼦子量量(Mn)は105
g/mol 以上
現時点では、分⼦子量量が数万程度度と⼩小さい
P
S OO
O
R2
M
R3
L
R1 R1
P上の置換基が分⼦子量量に与える
影響を検討する
15

16. P上の置換基が与える分⼦子量量への影響
Neuwald, B.; Falivene, L.; Caporaso, L.; Cavallo, L.; Mecking, S. Chem. Eur. J. 2013, 19, 17788.
MeO
OMe
Ar/(MeO)21
MeO
MeO
R1 = R2 =
O MeO
MeO
R1 = R2 =
cHexO/(MeO)21
Me
MeO
MeO
OMe
Me/(MeO)31
R1 = R2 =
MeO
OMe MeO MeO
MeO
MeO O F3C
MeO
MeO
OMe
iPrO
iPrO
P
S OO
O
Pd
Me
R1R2
R1 = R2 =
Ph1 Ar1 (MeO;Me2)1 (MeO)21
MeO1 cHexO1 H1 CF31 (MeO)31 (MeO)31
DOI: 10.1002/chem.201301365
Exploring Electronic and Steric Effects on the Insertion and Polymerization
Reactivity of Phosphinesulfonato PdII
Catalysts
Boris Neuwald,[a]
Laura Falivene,[b]
Lucia Caporaso,*[b]
Luigi Cavallo,[c]
and
Stefan Mecking*[a]
Introduction
The catalytic insertion polymerization of ethylene and pro-
pylene is one of the most well-studied chemical reactions. In
terms of applications, it is employed for the production of
more than 70 million tons of polyolefins annually. However,
an insertion polymerization of polar-substituted vinyl mono-
mers had remained elusive for a long time. Copolymeriza-
tion with ethylene was achieved for the first time with cat-
ionic PdII
diimine complexes. In this case, highly branched
copolymers are formed, which consist of ethylene as the
major component (!75 mol%) and contain acrylate units
situated preferentially at the ends of the branches.[1,2]
By
contrast, neutral arylphosphinesulfonato PdII
complexes co-
polymerize methyl acrylate (MA) and ethylene to linear
random copolymers.[3]
This catalyst system has recently at-
tracted much attention owing to the variety of polar mono-
mers that can be copolymerized with ethylene, including
acrylonitrile,[4,5]
vinyl acetate,[6]
and acrylic acid.[7,8]
Phos-
ACHTUNGTRENNUNGphinesulfonato PdII
methyl complexes are well-defined cata-
lyst precursors that can provide a convenient entry into the
catalytic cycle.[9]
For such complexes as (P^O)PdMe(L) (MeO
1-L; P^O=k2
-
P,O-(2-MeOC6H4)2PACHTUNGTRENNUNG(C6H4SO2O), Figure 1), the coordinat-
ing monodentate ligand L plays an important role for the
Abstract: Thirteen different symmetric
and asymmetric phosphinesulfonato
palladium complexes ([{(X
1-Cl)-m-M}n],
M=Na, Li, 1=X
ACHTUNGTRENNUNG(P^O)PdMe) were
prepared (see Figure 1). The solid-state
structures of the corresponding pyri-
dine or lutidine complexes were deter-
mined for (MeO)2
1-py, (iPrO)2
1-lut,
(MeO,Me2)
1-lut, (MeO)3
1-lut, CF3
1-lut, and
Ph
1-lut. The reactivities of the catalysts
X
1, obtained after chloride abstraction
with AgBF4, toward methyl acrylate
(MA) were quantified through deter-
mination of the rate constants for the
first and the consecutive MA insertion
and the analysis of b-H and other de-
composition products through NMR
spectroscopy. Differences in the homo-
and copolymerization of ethylene and
MA regarding catalyst activity and sta-
bility over time, polymer molecular
weight, and polar co-monomer incor-
poration were investigated. DFT calcu-
lations were performed on the main in-
sertion steps for both monomers to ra-
tionalize the effect of the ligand substi-
tution patterns on the polymerization
behaviors of the complexes. Full analy-
sis of the data revealed that: 1) elec-
tron-deficient catalysts polymerize with
higher activity, but fast deactivation is
also observed; 2) the double ortho-sub-
stituted catalysts (MeO)2
1 and (MeO)3
1
allow very high degrees of MA incor-
poration at low MA concentrations in
the copolymerization; and 3) steric
shielding leads to a pronounced in-
crease in polymer molecular weight in
the copolymerization. The catalyst
properties induced by a given P-aryl
(alkyl) moiety were combined effec-
tively in catalysts with two different
non-chelating aryl moieties, such as
cHexO/(MeO)2
1, which led to copolymers
with significantly increased molecular
weights compared to the prototypical
MeO
1.
Keywords: catalysis · coordination
modes · density-functional calcula-
tions · kinetics · reaction mecha-
nisms · theoretical chemistry
[a] Dr. B. Neuwald, Prof. Dr. S. Mecking
Chair of Chemical Materials Science, Department of Chemistry
University of Konstanz
78464 Konstanz (Germany)
Fax: (+49)7531-88-5152
E-mail: Stefan.Mecking@uni-konstanz.de
[b] Dr. L. Falivene, Dr. L. Caporaso
Department of Chemistry and Biology
FULL PAPER
Stefan Mecking
Universität Konstanz
16

17. P上の置換基の⽴立立体障害と官能基の効果
Anselment, T. M. J.; Wichmann, C.; Anderson, C. E.; Herdtweck, E.; Rieger, B. Organometallics 2011, 30, 6602.
■ P上の置換基の⽴立立体障害が分⼦子量量に影響を及ぼす傾向がある
P
S OO
O
Pd
Me
N
R1 R1
(0.01 mmol)
MeO
MeOR1 =
■ P上の置換基の官能基の影響は少ない
P
S OO
O
Pd
Me
N
R1 R1
X = 20
Mn = 1.8×103
Mw / Mn = 2.2
X = 5
Mn = 33×103
Mw / Mn = 1.7
n
toluene (30 ml), 50 ºC, 2 h
X bar
n
toluene (50 ml), 80 ºC, 1 h
30 atm
(0.01 mmol)
R1 =
MeO
Me
Mn = 19.1×103
Mw / Mn = 2.1
Mn = 18.8×103
Mw / Mn = 2.1
Vela, J.; Lief, G. R.; Shen, Z.; Jordan, R. F. Organometallics 2007, 26, 6624.
17

18. P上の置換基の⽴立立体障害と官能基の効果
(0.002 mmol)
n
toluene (100 ml), 80 ºC, 30 min
5 bar
AgBF4 (0.002 mmol)
置換基の⽴立立体障害と分⼦子量量についての
相関は得られなかったが
電⼦子供与性の置換基で分⼦子量量の
増⼤大が⾒見見られた
Neuwald, B.; Falivene, L.; Caporaso, L.; Cavallo, L.; Mecking, S. Chem. Eur. J. 2013, 19, 17788.
18
MeO
OMe
Ar1
P
S
O
O
O
Pd
Me
R1
R2
Cl
Na
2
R1 = R2 =
O MeO
MeO
R1 = R2 =
cHexO/(MeO)21

19. 配位⼦子と分⼦子量量の関係を解明する
Ota, Y.; Ito, S.; Kuroda, J.; Okumura, Y. W.; Nozaki, K. J. Am. Chem. Soc. 2014, 136, 11898.
P上のアルキル基の⽴立立体障害と分⼦子量量の相関を検討
従来では実現できなかった
⾼高分⼦子量量(>105
g/mol)の
直鎖コポリマーの合成を達成
Kyoko Nozaki
The Unversity of Tokyo
19
P
S OO
O
Pd
Me
N
R R

20. ジアルキルホスフィノ基を持つ配位⼦子
Ito, S.; Munakata, K.; Nakamura, A.; Nozaki, K. J. Am. Chem. Soc. 2009, 131, 14606.
■ 酢酸ビニルとエチレンの共重合
■ アリルモノマーとの重合
Ito, S.; Kanazawa, M.; Munakata, K.; Kuroda, J.; Nozaki, K. J. Am. Chem. Soc. 2011, 133, 1232.
P
S OO
O
Pd
Me
N
Cy Cy
(0.10 mmol)
O
toluene (3 ml)
80 ºC, 15 h12 ml Mn = 5.8×103
Mw / Mn = 2.3, i.r. = 1.9%
OAc
yx n
+
3.0 MPa
O
toluene (12 ml)
80 ºC, 3 h
3.0 ml Mn = 4.2×103
Mw / Mn = 2.3, i.r. = 0.9%
yx n
3.0 MPa
+
Cl
Cl
P
S OO
O
Pd
Me
N
Cy Cy
(0.10 mmol)
ラジカル重合では使⽤用できないアリルモノマーを⽤用いた共重合
FG
stable allyl radical
20

21. 今回検討する配位⼦子
P
S OO
O
Pd
Me
N
R R
Figure 1. Steric maps of palladium/alkyl
The P−Pd−O plane is placed in the xz
containing the Pd center. The methyl an
Scheme 1. Copolymerization of Et
Monomers 2a−f with Palladium/A
Catalysts 1a−f
Journal of the American Chemic
e 1. Steric maps of palladium/alkylphosphine−sulfonate complexes 1a−f. The Pd-atom is placed at the center of the xyz coordinate system (left).
−Pd−O plane is placed in the xz-plane with the z-axis bisecting the P−Pd−O angle. The y-axis represents the axial position of the xz-plane
nal of the American Chemical Society Communication
A, i-Pr B, t-Bu C, Cy D, 3-Pen E, 2,6-Dmhep F, Men
Pdまわりの⽴立立体障害の可視化 → Men基を持つが最も⼤大きな⽴立立体障害をもつ
re 1. Steric maps of palladium/alkylphosphine−sulfonate complexes 1a−f. The Pd-atom is placed at the center of the xyz coordinate system (left).
P−Pd−O plane is placed in the xz-plane with the z-axis bisecting the P−Pd−O angle. The y-axis represents the axial position of the xz-plane
rnal of the American Chemical Society Communication
ure 1. Steric maps of palladium/alkylphosphine−sulfonate complexes 1a−f. The Pd-atom is placed at the center of the xyz coordinate system (left).
e P−Pd−O plane is placed in the xz-plane with the z-axis bisecting the P−Pd−O angle. The y-axis represents the axial position of the xz-plane
urnal of the American Chemical Society Communication
gure 1. Steric maps of palladium/alkylphosphine−sulfonate complexes 1a−f. The Pd-atom is placed at the center of the xyz coordinate system (left).
he P−Pd−O plane is placed in the xz-plane with the z-axis bisecting the P−Pd−O angle. The y-axis represents the axial position of the xz-plane
urnal of the American Chemical Society Communication
Figure 1. Steric maps of palladium/alkylphosphine−sulfonate complexes 1a−f. The Pd-atom is placed at the center of the xyz coordinate system (left).
The P−Pd−O plane is placed in the xz-plane with the z-axis bisecting the P−Pd−O angle. The y-axis represents the axial position of the xz-plane
ournal of the American Chemical Society Communication
Figure 1. Steric maps of palladium/alkylphosphine−sulfonate complexes 1a−f. The Pd-atom is placed at the center of the xyz coordinate system (left).
The P−Pd−O plane is placed in the xz-plane with the z-axis bisecting the P−Pd−O angle. The y-axis represents the axial position of the xz-plane
Journal of the American Chemical Society Communication
Steric
Map
R =
■ ジアルキルホスフィノ基をもつ触媒は詳細な検討が未だなされていない
Figure 1. Steric maps of palladium/alkylphosphine−sulfonate complexes 1a−f. The Pd-atom is placed at the center of the xyz coordinate system (left).
The P−Pd−O plane is placed in the xz-plane with the z-axis bisecting the P−Pd−O angle. The y-axis represents the axial position of the xz-plane
Journal of the American Chemical Society Communication
R = Alkyl
Ota, Y.; Ito, S.; Kuroda, J.; Okumura, Y. W.; Nozaki, K. J. Am. Chem. Soc. 2014, 136, 11898.
21

22. エチレンの重合におけるP上の置換基の効果
P
S OO
O
Pd
Me
N
R R
R = Men で分⼦子量量が100×103
を超える
(0.010 mmol)
n
toluene (100 ml), 80 ºC, 1 h
3.0 MPa
Ota, Y.; Ito, S.; Kuroda, J.; Okumura, Y. W.; Nozaki, K. J. Am. Chem. Soc. 2014, 136, 11898.
entry
1
2
3
4
5
6
i-Pr
t-Bu
Cy
3-Pen
2,6-Dmhep
Men
yielda
(%)
6.41
18.6
11.5
1.25
1.97
2.05
activity
(g/mmol•h)
641
1860
1150
125
200
205
aIsolate yield. bMolecular Weights determined by SEC using polystyrene
standards, and universal calibration.
R
Mn
b
(×103 g/mol)
6.7
6.2
9.9
33
72
169
Mw/
Mn
b
2.7
4.1
2.4
2.4
2.4
1.5
22

23. エチレンの重合における置換基と分⼦子量量の相関
P
S OO
O
Pd
Me
N
R R
(0.010 mmol)
n
toluene (100 ml), 80 ºC, 1 h
3.0 MPa
R = MeO
OMe
Mn = 57–96×103 Mn = 169×103
⾼高分⼦子量量体を与えるビアリール系置換基よりも⾼高分⼦子量量体を与える
⽴立立体障害のパラメータと分⼦子量量の相関は…
sterimol
entry
1
2
3
4
5
6
i-Pr
t-Bu
Cy
3-Pen
2,6-Dmhep
Men
B5R
3.07
3.09
3.38
4.28
5.22
5.64
Ota, Y.; Ito, S.; Kuroda, J.; Okumura, Y. W.; Nozaki, K. J. Am. Chem. Soc. 2014, 136, 11898.
Haper, K. C.; Bess, E. N.; Sigman, M. S. Nat. Chem. 2012, 4, 366.
sterimol B5 パラメーターとほぼ⼀一致
23

24. アリルモノマーとの共重合における⽴立立体障害の相関
toluene (7.5 ml)
80 ºC, 3 h7.5 ml
yx n
3.0 MPa
+
OAc
OAc
P
S OO
O
Pd
Me
N
R R
(0.010 mmol)
entry
1
2
3
4
5
6
i-Pr
t-Bu
Cy
3-Pen
2,6-Dmhep
Men
yielda
(g)
0.35
0.31
0.30
0.36
0.35
1.65
activity
(g/mmol•h)
12
10
10
12
12
55
aIsolate yield. bMolecular Weights determined by SEC using polystyrene standards,
and universal calibration. cMolar incomporration ratios of allyl monomer determined
by 1H NMR analysis.
R
Mn
b
(×103 g/mol)
5.2
10.3
7.8
17
29
177
Mw/
Mn
b
2.4
5.1
2.0
2.4
2.8
2.0
i.r.c
1.9
0.6
1.8
1.5
1.1
0.6
Ota, Y.; Ito, S.; Kuroda, J.; Okumura, Y. W.; Nozaki, K. J. Am. Chem. Soc. 2014, 136, 11898.
共重合においても分⼦子量量が100×103
を超える
24

25. さまざま極性モノマーとの共重合
Ota, Y.; Ito, S.; Kuroda, J.; Okumura, Y. W.; Nozaki, K. J. Am. Chem. Soc. 2014, 136, 11898.
entry
1
2
3
4
5
6
7
8
9
10
11
12
13
14
yielda
(g)
1.65
1.05
1.10
0.48
0.30
0.35
2.02
0.88
0.44
0.24
1.61
1.30
0.30
0.34
activity
(g/mmol•h)
55
35
37
16
2.3
2.2
67
29
15
1.6
54
8.6
2.0
2.3
aIsolate yield. bMolecular Weights determined by SEC using polystyrene standards, and universal calibration.
cMolar incomporration ratios of allyl monomer determined by 1H NMR analysis.
comonomer
Mn
b
(×103 g/mol)
177
47
86
36
17
33
72
40
8.5
6.1
15
11
14
4.8
Mw/
Mn
b
2.0
2.2
2.1
1.7
2.0
2.3
2.5
2.0
2.0
1.8
4.1
2.4
1.9
2.7
i.r.c
0.6
2.5
2.2
5.1
7.8
0.6
1.4
3.0
8.3
11
1.1
7.7
0.7
1.3
ethylene
(MPa)
3.0
3.0
2.1
1.0
1.0
3.0
3.0
2.0
1.0
1.0
3.0
1.0
3.0
3.0
monomer
(mL)
7.5
7.5
7.5
7.5
12
3
7.5
7.5
7.5
12
7.5
12
7.5
12
solvent
(mL)
7.5
7.5
7.5
7.5
3
12
7.5
7.5
7.5
3
7.5
3
7.5
3
T
(ºC)
80
100
80
100
100
80
80
80
100
100
80
100
80
80
t
(h)
3
3
3
3
13
16
3
3
3
15
3
15
15
15
CH2OAc
CH2Cl
CO2Me
OBu
CN
OAc
P
S OO
O
Pd
Me
N
R R
(0.010 mmol)
R =
X+ toluene (7.5 ml)
temp, time X
yx n
25

26. Men基の共重合における分⼦子量量に対する効果
Ota, Y.; Ito, S.; Kuroda, J.; Okumura, Y. W.; Nozaki, K. J. Am. Chem. Soc. 2014, 136, 11898.
allyl acetate (R = Men)
metyl acrylate(R = Men)
allyl acetate (R = Cy)
methyl acrylate (R = 2-MeO-C6H4)
様々なモノマー⽐比においてMen基の効果が表れている
Ito, S.; Kanazawa, M.; Munakata, K.; Kuroda, J.; Nozaki, K. J. Am. Chem. Soc. 2011, 133, 1232.
Drent, E.; van Dijk, R.; van Ginkel, R. van Oort, B.; Pugh, R. I. Chem. Commun. 2002, 744.
26

27. まとめ
P
S OO
O
Pd
Me
N
R R
ホスフィン­−スルホン酸配位⼦子はさまざまな
極性ビニルモノマーとエチレンを共重合させることが可能。
配位⼦子の⽴立立体障害を調節することで⾼高分⼦子量量(>105
)の合成を達成。
さらなる、重合機構の解明、新材料料の開発が期待される
強いトランス効果に
よる錯体の⽴立立体の固定
⾮非対称な配位座を
もつことで重合機構
をコントロール
中⼼心⾦金金属からやや離離れた
場所の⽴立立体障害が効果的
27
resulting polyethylenes remained relatively low (Mn < 10 × 103
g/mol, entries 1−3 in Table 1). When bulkier ligands such as 1d
(3-Pen), 1e (2,6-Dmhep), and 1f (Men) were used, the Mn of the
polyethylenes increased to 33 × 103
, 72 × 103
, and 169 × 103
g/
mol, respectively, albeit with lower catalytic activity than 1a−c.
The exceptionally high Mn values achieved with catalyst 1f even
exceeded those gained by bis(2′,6′-dimethoxy-1,1′-biphenyl-2-
yl)phosphine−sulfonate (Mn = 57 × 103
−96 × 103
g/mol, after
ium/alkylphosphine−sulfonate complexes 1a−f. The Pd-atom is placed at the center of the xyz coordinate system (left).
in the xz-plane with the z-axis bisecting the P−Pd−O angle. The y-axis represents the axial position of the xz-plane
methyl and 2,6-lutidine groups were omitted for the analysis of the steric maps.
on of Ethylene and Polar
adium/Alkylphosphine−Sulfonate
Chemical Society Communication
Steric
Map

28. ジアリールホスフィノ基の⽴立立体障害
resulting polyethylenes remained relatively low (Mn < 10 × 103
g/mol, entries 1−3 in Table 1). When bulkier ligands such as 1d
(3-Pen), 1e (2,6-Dmhep), and 1f (Men) were used, the Mn of the
polyethylenes increased to 33 × 103
, 72 × 103
, and 169 × 103
g/
mol, respectively, albeit with lower catalytic activity than 1a−c.
The exceptionally high Mn values achieved with catalyst 1f even
exceeded those gained by bis(2′,6′-dimethoxy-1,1′-biphenyl-2-
yl)phosphine−sulfonate (Mn = 57 × 103
−96 × 103
g/mol, after
universal calibration18
).3b,f
To gain a deeper understanding, we
te complexes 1a−f. The Pd-atom is placed at the center of the xyz coordinate system (left).
xis bisecting the P−Pd−O angle. The y-axis represents the axial position of the xz-plane
ps were omitted for the analysis of the steric maps.
r
Sulfonate
Communication
P
S OO
O
Pd
Me
R1 R1
optimization by
BP86/6-‐‑‒31G(d)+Lanl2dz
X-‐‑‒ray structure
P
S OO
O
Pd
R1 R1
R = MeO
OMe

29. Figure S2. Taft Es parameters Figure S3. Correlation with %Vbur par
iPr
Cy
3-Pen
DmHep
tBu
1
10
-4 -3 -2 -1
Mn(103)
Taft param. (Es)
iPr
Cy
DmHep
M
tBu
3-Pen
1
10
100
46 48 50 52
Mn(103)
%VBur
iPr
tBu
Cy
3-Pen
DmHep
Men
1
10
100
1000
1 1.5 2 2.5 3
Mn(103)
B1
iPr
tBu
Cy
3-Pen
M
DmHep
1
10
100
1000
2 3 4 5
Mn(103)
ジアリールホスフィノ基の⽴立立体障害The correlations between the steric parameters and the molecular weights are shown below.
Figure S2. Taft Es parameters Figure S3. Correlation with %Vbur parameters
iPr
Cy
3-Pen
DmHep
tBu
1
10
100
-4 -3 -2 -1
Mn(103)
Taft param. (Es)
iPr
Cy
DmHep
Men
tBu
3-Pen
1
10
100
1000
46 48 50 52 54
Mn(103)
%VBur
iPr
tBu
Cy
3-Pen
DmHep
Men
1
10
100
1000
1 1.5 2 2.5 3
Mn(103)
iPr
tBu
Cy
3-Pen
Men
DmHep
1
10
100
1000
2 3 4 5 6
Mn(103)
e correlations between the steric parameters and the molecular weights are shown below.
Figure S2. Taft Es parameters Figure S3. Correlation with %Vbur parameters
iPr
Cy
3-Pen
DmHep
tBu
1
10
100
-4 -3 -2 -1
Mn(103)
Taft param. (Es)
iPr
Cy
DmHep
Men
tBu
3-Pen
1
10
100
1000
46 48 50 52 54
Mn(103)
%VBur
iPr
tBu
Cy
3-Pen
DmHep
Men
1
10
100
1000
1 1.5 2 2.5 3
Mn(103)
iPr
tBu
Cy
3-Pen
Men
DmHep
1
10
100
1000
Mn(103)

30. %Vburとは
中⼼心⾦金金属から指定された半径内の
分⼦子の体積の詰まりの程度度を表す
https://www.molnac.unisa.it/OMtools/sambvca.php 12月9日閲覧

31. Steric Mapの⾒見見⽅方
%Vburから求められる錯体の
中⼼心⾦金金属まわりの⽴立立体障害の可視化
Poater, A. et al. Procedia Computer Science. 2013, 18. 845.

32. Sterimolパラメータの計算
X線構造解析の結果に基づいてソフトウェア：Mol2Molを⽤用いて計算
http://www.gunda.hu/mol2mol/m2m/index.html 12⽉月7⽇日閲覧entry
1
2
3
4
5
i-Pr
t-Bu
Cy
2-bu
2,6-Dmhep
B5R
3.17
3.17
3.49
4.01
5.47
⽂文献値
Hansch, C.; Leo, A. Explording QSAR: Fundamentals and Applications in Chemistry
and Biology; American Chemical Society: Washington, DC, 1995.

33. 速度度論論的にはトランス体が安定
R = 2-MeO-C6H4
quant.
trans : cis = 4 : 1
PR2
S ONaO
O
Pd
Cl
Cl
Pd
N
Me
N
Me
+ CD2Cl2, –25 ºC
P
S OO
O
Pd
Me
R1 R1
N P
S OO
O
Pd
Me
N
R1 R1
+
CD2Cl2, –25 ºC
P
S OO
O
Pd
Me
N
R1 R1
cis only
Zhou, X.;Lau, K.-C..;Petro, B. J.; Jordan, R. F. Organometallics. 2014, ASAP.

34. M
L1
L3L2
L4
トランス影響 → 熱⼒力力学的安定（静的トランス効果）
トランス効果 → 速度度論論的安定性（動的トランス効果）
平⾯面四配位錯体においてある配位⼦子が
トランス位の配位⼦子に影響を与える現象
例例：L1が強いσドナー性 (アルキル基など）
↓
L３はアニオン性配位⼦子が有利利

35. ホスフィンオキサイドでも反応は進⾏行行
Carrow. B. P.; Nozaki, K. J. Am. Chem. Soc. 2012, 134, 8802.

36. 全体の反応機構
Noda, S.; Nakamura, A.; Kochi, T.; Chung, L. W.; Morokuma, K.; Nozaki, K. J. Am. Chem. Soc. 2009, 131, 14088.

37. 共重合におけるエネルギー計算
Nozaki, K.; Kusumoto, S.; Noda, S.; Kochi, T.; Chung, L. W.; Morokuma, K. J. Am. Chem. Soc. 2010, 132, 16031.

38. 共重合におけるエネルギー計算
Nozaki, K.; Kusumoto, S.; Noda, S.; Kochi, T.; Chung, L. W.; Morokuma, K. J. Am. Chem. Soc. 2010, 132, 16031.