Phosphine phosphonic amide nickel catalyzed ethylene polymerization and copolymerization with polar monomers

Article abstract of DOI:10.1039/c8dt01018h

The phosphine phosphonic amide ligand platform is highly versatile, with three positions that can be independently tuned. In this contribution, we wish to study the nickel complexes based on this ligand system. Interestingly, the nickel dibromide and nick

Full text of DOI:10.1039/c8dt01018h

View Article Online
View Journal
Dalton
Transactions
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: C. Hong, X. Sui, Z.
Li , W. Pang and M. Chen, Dalton Trans., 2018, DOI: 10.1039/C8DT01018H.
This is an Accepted Manuscript, which has been through the
Volume 45 Number
1 7 January 2016 Pages 1–398
Royal Society of Chemistry peer review process and has been
accepted for publication.
Dalton
Transactions
Accepted Manuscripts are published online shortly after
An international journal of inorganic chemistry
www.rsc.org/dalton
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
rsc.li/dalton

Please do not adjust margins
Dalton Transactions
Page 1 of 5
View Article Online
DOI: 10.1039/C8DT01018H
Dalton Transactions
PAPER
Phosphine Phosphonic Amide Nickel Catalyzed Ethylene
Polymerization and Copolymerization with Polar Monomers†
Changwen Hong, ‡a Xuelin Sui, ‡a Ziqian Li, b Wenmin Panga and Min Chen,*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
The phosphine phosphonic amide ligand platform is highly versatile, with three positions that can be independently tuned.
In this contribution, we wish to study the nickel complexes based on this ligand system. Interestingly, the nickel dibromide
and the nickel allyl complexes are not active in ethylene polymerization. In contrast, the nickel phenyl chloride complexes
are highly active in ethylene polymerization in the presence of sodium tetrakis(3,5ꢀbis(trifluoromethyl)phenyl)borate
cocatalyst. In addition, these nickel complexes can initiate ethylene copolymerizations with polar functionalized
comonomers including methyl 10ꢀundecenoate, 6ꢀchloroꢀ1ꢀhexene and 5ꢀacetoxyꢀ1ꢀpentene. More interestingly, these
nickel complexes can oligomerize 1ꢀhexene and 6ꢀchloroꢀ1ꢀhexene.
www.rsc.org/
Introduction
In olefin polymerization, late transition metal catalysts possess the
advantage of low oxophilicity versus their early transition metal
counterparts. Therefore, they are potentially applicable to
incorporate polar functionalized comonomers during olefin
polymerization. For the copolymerization purpose, the metal
palladium has been the dominant player. For example, the Brookhart
type αꢀdiimine palladium catalyst is a milestone discovery in this
field (Chart 1, I),1 which can copolymerize ethylene with acrylates,
silyl vinyl ethers and a number of other polar monomers.2 In
contrast, the αꢀdiimine nickel counterpart shows much narrower
polar monomer substrate scope, and usually requires a large amount
of aluminum cocatalysts.3 The Drent type phosphineꢀsulfonate
palladium catalyst (Chart 1, II) can enable the copolymerizations of
ethylene with a variety of polar monomers.4 However, the nickel
counterpart has only recently been demonstrated with the
copolymerization capabilities, and with very narrow substrate
scope.5
Chart 1 Some recently reported high performance palladium and
nickel catalysts.
Nꢀheterocyclic carbene based nickel catalysts (Chart 1, V),8 and
diphosphazane monoxide nickel catalysts (Chart 1, VI)9 can
copolymerize ethylene with some polar monomers. We recently
showed that some cationic phosphine phosphonic amide palladium
complexes (Chart 1, VII) are highly active in ethylene
polymerization, and are capable of copolymerizing ethylene with
polar monomers such as methyl acrylate, vinyl butyl ether and allyl
acetate.10 A great advantage of this catalyst system is that three
positions (R1, R2 and R3) can be independently adjusted, making it
highly versatile to tune the properties of the metal catalysts. In this
contribution, we decide to investigate the synthesis, characterization
and polymerization properties of the phosphine phosphonic amide
nickel complexes.
The intrinsically higher oxophilicity of the nickel metal makes it
highly challenging to design high performance nickel catalyst for the
polar monomer problem. In recent years, there have been some great
advances in this aspect. For example, salicylaldimine nickel catalysts
(Chart
1,
III),6
SHOP
type
(Shell Higher Olefin Process) nickel catalysts (Chart 1, IV),7
aDepartment of Polymer Science and Engineering, University of Science and
Technology of China, Hefei, 230026, China. E-mail: misschen@ustc.edu.cn
bUndergraduate Department, University of Chinese Academy of Sciences, Beijing,
100049, China
Results and Discussions
†Electronic Supplementary Information (ESI) available: CCDC 1843013 (Ni1-Br),
1843014 (Ni1), 1822275 (Ni3). [details of any supplementary information available
should be included here]. See DOI: 10.1039/x0xx00000x
The phosphine phosphonic amide ligands L1 and L2 have been
reported by us, and the ligand L3 bearing biaryl substituent was preꢀ
‡
These authors contributed equally to this work.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2018, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 2 of 5
View Article Online
DOI: 10.1039/C8DT01018H
ARTICLE
Journal Name
Figure 1 Molecular structures of Ni1-Br (a), Ni1 (b), Ni3 (c).
Hydrogen atoms have been omitted for clarity. (a) Selected bond
distances (Å) and angles (deg) for Ni1-Br: Ni1ꢀBr1 2.3670(14), Ni1ꢀ
Br2 2.3381(13), Ni1ꢀO1 1.957(5), Ni1ꢀP2 2.281(2), P1ꢀO1 1.504(5),
P1ꢀN1 1.632(6); O1ꢀNi1ꢀP2 85.99(15), O1ꢀNi1ꢀBr2 112.78(15), P2ꢀ
Ni1ꢀBr2 118.42(7), O1ꢀNi1ꢀBr1 108.47(16), P2ꢀNi1ꢀBr1 98.62(7),
Br2ꢀNi1ꢀBr1 125.17(6). (b) Selected bond distances (Å) and angles
(deg) for Ni1: Ni1ꢀC31 1.861(4), Ni1ꢀO1 1.968(3), Ni1ꢀP2
2.1590(12), Ni1ꢀCl1 2.1966(13), N1ꢀP1 1.635(3), O1ꢀP1 1.499(3);
C31ꢀNi1ꢀO1 168.55(17), C31ꢀNi1ꢀP2 95.53(13), O1ꢀNi1ꢀP2
83.72(8), C31ꢀNi1ꢀCl1 91.48(13), O1ꢀNi1ꢀCl1 91.97(8), P2ꢀNi1ꢀCl1
165.10(5). (c) Selected bond distances (Å) and angles (deg) for Ni3:
Ni1ꢀC39 1.898(7), Ni1ꢀO3 1.946(4), Ni1ꢀP1 2.1450(19), Ni1ꢀCl1
2.209(2), P2ꢀO3 1.508(4), P2ꢀN1 1.640(5); C39ꢀNi1ꢀO3 173.9(3),
C39ꢀNi1ꢀP1 90.0(2), O3ꢀNi1ꢀ P1 93.35(14), C39ꢀNi1ꢀCl1 87.7(2),
O3ꢀNi1ꢀCl1 89.66(14), P1ꢀNi1ꢀCl1 171.62(9).
Scheme 1 Synthesis of the phosphine phosphonic amide ligands and
the corresponding nickel complexes.
pared using similar procedure (Scheme 1).10 The biaryl substituent
has been shown by Scott and our group to enhance the polymer
molecular weight in the phosphineꢀsulfonate nickel system.11,5 Since
this is a neutral ligand system similar as the αꢀdiimine system, our
initial target is nickel dibromide complex. Complex Ni1-Br can be
obtained from the reaction of ligand L1 with
1 equiv. of
(DME)NiBr2 (DME = ethylene glycol dimethyl ether). However, the
addition of methylaluminoxane (MAO) cocatalyst led to the
decomposition of this nickel complex, and no activity was observed
in ethylene polymerization. Subsequently, the cationic nickel allyl
species Ni1-allyl was generated from the reaction of the ligand L1
with [(allyl)NiCl]2 and sodium tetrakis(3,5ꢀbis(trifluoromethyl)
phenyl)borate (NaBAF). However, this complex is not active either
in ethylene polymerization, which may be due to the strong
complexation of the allyl moiety to the nickel center. When
coacatalyst MAO or B(C6F5)3 was added, Ni1-allyl showed very low
activities in ethylene polymerization (Table S1). Eventually, the
nickel phenyl species Ni1-Ni3 were prepared from the reactions of
L1-L3 with bis(1,5ꢀcyclooctadiene)nickel and PhCl. These nickel
(Table 1, entry 6). Complex Ni3 remained active for ethylene
polymerization for 4 h at 30oC and 80oC (Figure S1, S2). The
melting points of the polyethylene samples are all above 110 oC,
suggesting that they possess relatively linear microstructure. High
temperature H NMR analysis (Figures S10 and S11) showed that
the branching densities of the polyethylene samples generated by
Ni3 are 25 (at 80 oC) and 4 (at 30 oC) per 1000 carbon atoms.
The properties of these nickel complexes in ethyleneꢀpolar
comonomer copolymerizations were also studied. Unfortunately,
some fundamental polar monomers such as methyl acrylate or vinyl
acetate completely shut down the ethylene polymerization. When
some spacers were put between the double bond and the polar
groups, these nickel complexes can incorporate the polar
comonomers during ethylene polymerization. For example, methyl
1
1
complexes were characterized with H NMR, 13C NMR, 31P NMR
and elemental analysis.
The molecular structures of Ni1-Br, Ni1 and Ni3 were
determined by Xꢀray diffraction analysis (Figure 1). These data show
that, Ni1-Br, Ni1 and Ni3 were intergrated as twinning. The Ni
center adopts distorted tetrahedron geometry in Ni1-Br, and square
planar geometry in Ni1/Ni3. The R1 and R2 substituents reside at the
equatorial and axial position of the phosphorus atom. In the structure
of Ni3, the biaryl substituent forms πꢀπ stacking with the ligand
benzo backbone. This could increase the rigidity of the catalyst
structure and potentially improve catalyst properties.12 All of these
nickel complexes are highly active in ethylene polymerization when
activated using 1.2 equiv. of NaBAF (Table 1). The activities can
reach well above 106 g·molꢀ1·hꢀ1, making them among the most
active nickel catalysts in ethylene homopolymerization.13 Ni1 and
Ni2 can only generate polyethylene with molecular weight of a few
thousand (Table 1, entries 1ꢀ4). For the case of Ni3 bearing biaryl
substituent, the polyethylene molecular weight can reach 29,000
Table 1 Ethylene homopolymerization with Ni1-Ni3a
c
d
Ent. Cat. cat
T
t
Yield Act.b
Tm
Mn
PDId
(ꢁmol) (oC) (h) (g)
(oC)
112
115
112
126
121
133
(104)
0.15
0.21
0.16
0.37
0.61
2.9
1
2
3
4
5
6
Ni1
Ni1
Ni2
Ni2
Ni3
Ni3
1
1
1
1
1
1
80
30
80
30
80
30
1
2
1
2
1
2
3.6
2.2
2.8
2.0
1.2
0.2
36
11
2.3
2.6
2.0
2.5
3.3
3.0
28
10
12
1.0
aPolymerization conditions: 18 mL toluene, 2 mL dichloromethane,
9 atm ethylene pressure, 1.2 eq. NaBAF. Activity is in unit of 105
b
g·molꢀ1·hꢀ1. Determined by differential scanning calorimetry, third
c
heating. dDetermined by GPC using universal calibration.
2 | J. Name., 2018, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 3 of 5
View Article Online
DOI: 10.1039/C8DT01018H
Journal Name
ARTICLE
Table 2 Ethylene/polar monomer copolymerizations with Ni1-Ni3.a
d
e
Ent.
Cat.
Comonomer
[M]
mol/L
1
Yield
(g)
Act.b
Incorpc
(%)
Tm
Mn
PDIe
Aver Como
of per Chainf
0.09
(oC)
99
(103)
1.3
1
2
3
4
5
6
7
8
Ni1
Ni2
Ni3
Ni3
Ni3
Ni3
Ni3
Ni3
0.4
0.10
0.13
0.85
0.13
0.03
1.50
0.50
0.08
0.2
1.8
1.9
3.5
1.9
1.6
2.4
2.5
2.0
1
1
2
3
1
2
3
0.5
3.4
0.5
0.1
6.0
2.0
0.3
0.3
0.6
2.6
3.3
0.8
1.3
2.9
109
118
102
ꢀ
1.6
5.1
1.4
1.2
2.2
1.6
1.5
0.17
1.05
1.12
1.18
0.61
0.71
1.42
116
114
107
9
Ni3
1
0.1
0.03
1.2
ꢀ
2.0
2.7
0.82
10g
11g
Ni3
Ni3
1
1
0.8
2.4
0.20
0.60
0.3
0.4
129
125
27
25
3.8
3.4
2.84
3.53
aPolymerization conditions: 18 mL toluene, 2 mL dichloromethane, 9 atm ethylene pressure, 1.2 eq. NaBAF, 20 ꢁmol catalyst, 2 h, 80 oC. bActivity is
in unit of 105 g·molꢀ1·hꢀ1. c Determined by 1H NMR spectroscopy. dDetermined by differential scanning calorimetry, third heating. eDetermined by
GPC using universal calibration. fAver Como of per Chain = Average number of cmonomer units of per chain. gCopolymerization at 30 oC.
10ꢀundecenoate, 6ꢀchloroꢀ1ꢀhexene and 5ꢀacetoxyꢀ1ꢀpentene are all molecular weight polymer. In contrast, high molecular weight
suitable substrates (Table 2). Ni3 showed much better performance polymer obtained at 30oC (Table 2, entry 10ꢀ11) are true copolymers.
than Ni1 and Ni2, in terms of comonomer incorporation ratios and
copolymer molecular weights (Table 2, entries 1ꢀ3). At higher substrates considering their electronic and steric parameters. Thereꢀ
comonomer concentration, the activity and copolymer molecular fore, transition metal catalyzed polar comonomer
Comparing with ethylene, polar comonomers are much worse
weight were greatly reduced, while the comonomer incorporation homopolymerization is even more challenging than their
ratio can be increase to 3.3% (Table 2, entries 3ꢀ5). Similar copolymerization with ethylene. In literature, there have been very
performances were observed in Ni3 catalyzed ethylene few successful examples in this regard.9,14 Base on literature
copolymerizations with 6ꢀchloroꢀ1ꢀhexene and 5ꢀacetoxyꢀ1ꢀpentene reports15 and our experiences, the phosphineꢀsulfonate palladium and
(Table 2, entries 6ꢀ9). At lower copolymerization temperature (30 oC, phosphineꢀsulfonate nickel catalysts cannot oligomerize 1ꢀhexene or
Table 2, entries 10 and 11), the copolymer molecular weight can be 6ꢀchloroꢀ1ꢀhexene. Quite interestingly, Ni1 and Ni2 can oligomerize
greatly enhanced (Mn up to 27,000). Through the calculated average 1ꢀhexene and 6ꢀchloroꢀ1ꢀhexene to generate oligomers with
number of comonomer units of per chain, we can see that these molecular weights of a few thousand (Table 3, entries 1ꢀ4). Ni3 is
polymeric products are generally mixtures of copolymer and homoꢀ not active at all, which is probably due to steric effect. Currently, the
polymer in varying degrees (Table 2, entry 1ꢀ9). The reason is that exact reason is not fully understood. This could be due to the
fast chain transfer of metal center at 80oC leads to comparatively low cationic and high electrophilicity nature, as well as the sterically
open feature of this system. Although, the PDI values (1.1ꢀ1.3) are
very low, oligomerization of 1ꢀhexene and 6ꢀchloroꢀ1ꢀhexene do not
show living behaviors.
Table 3 1ꢀhexene and 6ꢀchloroꢀ1ꢀhexene oligomerization with Ni1-
Ni3.a
c
Conclusions
Ent.
Cat. αꢀolefin
Yield
(mg)
80
Act.b
Mn
(103)
2.3
PDIc
In summary, some phosphine phosphonic amide nickel complexes
have been prepared and characterized. The choice of metal
precursors is critical to obtain high performance polymerization
catalyst. Specifically, the nickel phenyl chloride complexes (Ni1ꢀ
Ni3) combined with NaBAF are highly active in ethylene
polymerization with activities up to 3.6 × 106 g·molꢀ1·hꢀ1, generating
polyethylene with molecular weights of up to 29,000 and melting
1
2
3
4
5
6
Ni1
Ni1
Ni2
Ni2
Ni3
Ni3
0.67
0.17
0.83
0.25
ꢀ
1.1
1.2
1.3
1.1
ꢀ
20
100
30
0.8
4.3
2.6
ꢀ
trace
trace
ꢀ
ꢀ
ꢀ
o
points of up to 133 C. In ethylene copolymerizations with methyl
aPolymerization conditions: 10 ꢁmol Ni catalyst, 4 mL toluene, 0.5 mL
dichloromethane, 1 mol/L comonomer, 30 oC, 12 hours, 1.2 eq. NaBAF.
bActivity is in unit of 103 g·molꢀ1·hꢀ1. cDetermined by GPC using
universal calibration.
10ꢀundecenoate, 6ꢀchloroꢀ1ꢀhexene and 5ꢀacetoxyꢀ1ꢀpentene,
activities of up to 1.5 × 105 g·molꢀ1·hꢀ1 could be achieved, along with
moderate comonomer incorporations (0.2ꢀ3.3%) and moderate
copolymer molecular weights (1,200ꢀ27,000). Interestingly, this
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2018, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 4 of 5
View Article Online
DOI: 10.1039/C8DT01018H
ARTICLE
Journal Name
Takeuchi, Y. Chiba, S. Takano and K. Osakada, Angew. Chem.
Int. Ed., 2013, 52, 12536.
nickel system possesses unique capabilities of being able to
oligomerize polar monomers such as 6ꢀchloroꢀ1ꢀhexene.
7
(a) U. Klabunde and S. D. Ittel, J. Mol. Catal., 1987, 41, 123;
(b) U. Klabunde and W. Chester, Pa. 1987, US 4, 698, 403; (c)
B. S. Xin, N. Sato, A. Tanna, Y. Oishi, Y. Konishi and F.
Shimizu, J. Am. Chem. Soc., 2017, 139, 3611.
W. Tao, R. Nakano, S. Ito and K. Nozaki, Angew. Chem. Int.
Ed., 2016, 55, 2835.
Conflicts of interest
There are no conflicts to declare.
8
9
Acknowledgements
M. Chen and C. L. Chen, Angew. Chem. Int. Ed., 2018, 57,
3094.
This work was supported by the National Natural Science
Foundation of China (NSFC, 21704094), the Chinese Postdoctoral
Science Foundation (2017M612076) and Fundamental Research
Funds for the Central Universities (WK2060200025).
10 X. L. Sui, S. Y. Dai and C. L. Chen, ACS Catal., 2015, 5, 5932.
11 P. Perrotin, J. S. J. McCahill, G. Wu and S. L. Scott, Chem.
Commun., 2011, 47, 6948.
12 (a) G. Z. Song, W. M. Pang, M. Chen and C. L. Chen, Poly.
Chem., 2017, 8, 7400; (b) B. P. Yang, S. Y. Xiong and C. L.
Chen, Poly. Chem., 2017, 8, 6272. (c) C. Zou, W. M. Pang and
C. L. Chen, Sci. China Chem., 2018, DOI/10.1007/s11426ꢀ018ꢀ
9237ꢀ6.
13 H. L. Mu, L. Pan, D. P. Song and Y. S. Li, Chem. Rev., 2015,
115, 12091.
14 (a) C. Chen, S. Luo and R. F. Jordan, J. Am. Chem. Soc., 2008,
130, 12892; (b) D. Guironnet, P. Roesle, T. Rünzi, I. Göttkerꢀ
Schnetmann and S. Mecking, J. Am. Chem. Soc., 2009, 131,
422.
References
1
(a) L. K. Johnson, C. M. Killian and M. Brookhart, J. Am.
Chem. Soc., 1995, 117, 6414; (b) Z. Guan, P. M. Cotts, E. F.
McCord and S. J. McLain, Science, 1999, 283, 2059; (c) Z. Ye,
L. Xu, Z. Dong and P. Xiang, Chem. Commun., 2013, 49, 6235;
(d) D. Takeuchi, Polym. J., 2012, 44, 919; (e) L. H. Guo and C.
L. Chen, Sci. China. Chem., 2015, 58, 1663; (f) L. H. Guo, S. Y.
Dai, X. L. Sui and C. L. Chen, ACS Catal., 2016, 6, 428; (g) L.
H. Guo, W. Liu and C. L. Chen, Mater. Chem. Front., 2017, 1,
2487.
2
(a) L. K. Johnson and S. Mecking, J. Am. Chem. Soc., 1996,
118, 267; (b) C. L. Chen, S. J. Luo and R. F. Jordan, J. Am.
Chem. Soc., 2010, 132, 5273; (c) S. Y. Dai, X. L. Sui and C. L.
Chen, Angew. Chem. Int. Ed., 2015, 54, 9948; (d) S. Y. Dai and
C. L. Chen, Angew. Chem. Int. Ed., 2016, 55, 13281; (e) S. Y.
Dai, S. X. Zhou, W. Zhang and C. L. Chen, Macromolecules,
2016, 49, 8855. (f) X. L. Sui, C. W. Hong, W. M. Pang and C.
L. Chen, Mater. Chem. Front., 2017, 1, 967; (g) Z. Chen, W.
Liu, O. Daugulis and M. Brookhart, J. Am. Chem. Soc., 2016,
138, 16120.
15 S. Noda, A. Nakamura, T. Kochi, L. W. Chung, K. Morokuma
and K. Nozaki, J. Am. Chem. Soc., 2009, 131, 14088.
3
(a) L. K. Johnson, L. Wang, S. McLain, A. Bennett, K. Dobbs,
E. Hauptman, A. Ionkin, S. D. Ittel, K. Kutnisky, W. Marshall,
E. McCord, C. Radzewich, A. Rinehart, K. J. Sweetman, Y. Wꢀ
ang, Z. Yin and M. Brookhart, ACS Aymp. Ser., 2003, 857, 131;
(b) B. K. Long, J. M. Eagan, M. Mulzer and G. W. Coates, An-
gew. Chem. Int. Ed., 2016, 55, 7106; (c) L. Zhong, G. Li, G. Liꢀ
ang, H. Gao and Q. Wu, Macromolecules, 2017, 50, 2675; (d)
M. Li, X. B. Wang, Y. Luo and C. L. Chen, Angew. Chem. Int.
Ed., 2017, 56, 11604; (e) Z. Chen, M. D. Leatherman, O. Daugꢀ
ulis and M. Brookhart, J. Am. Chem. Soc., 2017, 139, 16013; (f)
S. X. Zhou and C. L. Chen, Science Bulletin, 2018, 63, 441.
(a) A. Nakamura, T. M. J. Anselment, J. Claverie, B. Goodall, R.
F. Jordan, S. Mecking, B. Rieger, A. Sen, P. W. N. M. Van
Leeuwen and K. Nozaki, Acc. Chem. Res., 2013, 46, 1438; (b)
B. Neuwald, L. Caporaso, L. Cavallo and S. Mecking, J. Am.
Chem. Soc., 2013, 135, 1026; (c) Y. Ota, S. Ito, M. Kobayashi,
S. Kitade, K. Sakata, T. tayano and K. Nozaki, Angew. Chem.
Int. Ed., 2016, 55, 7505.
4
5
6
(a) S. Ito, Y. Ota and K. Nozaki, Dalton. Trans., 2012, 41,
13807; (b) M. Chen and C. L. Chen, ACS Catal., 2017, 7, 1308;
(c) T. Liang and C. L. Chen, Organometallics, 2017, 36, 2338.
(a) T. R. Younkin, E. F. Connor, J. I. Henderson, S. K.
Friedrich, R. H. Grubbs and D. A. Bansleben, Science, 2000,
287, 460; (b) M. R. Radlauer, A. K. Buckley, L. M. Henling
and T. Agapie, J. Am. Chem. Soc., 2013, 135, 3784; (c) M. P.
Weberski, C. L. Chen, M. Delferro and T. J. Marks, Chem. Eur.
J., 2012, 18, 10715; (d) A. Osichow, I. GöttkerꢀSchnetmann
and S. Mecking, Organometallics, 2013, 32, 5239; (e) D.
4 | J. Name., 2018, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Page 5 of 5
Dalton Transactions
View Article Online
DOI: 10.1039/C8DT01018H
Journal Name
ARTICLE
R1
P
R2
n
Ph
X
Ni
+
iPr
iPr
P O
Ph
Cl
n
m
X
N
X
X
+ NaBAF
n
Table of Contents
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2018, 00, 1-3 | 5
Please do not adjust margins