Monomeric nickel hydroxide stabilized by a sterically demanding phosphorus-nitrogen PN3P-pincer ligand: synthesis, reactivity and catalysis

Article abstract of DOI:10.1039/c8dt03403f

A terminal nickel hydroxide complex (PN³P)Ni(OH) (3) bearing the 2^nd generation phosphorus-nitrogen PN³P-pincer ligand has been synthesized and structurally characterized. As a nucleophile, 3 reacts with CO to afford the hydroxycarbonyl complex 4, (PN³P)Ni(COOH). 3 can also activate CO₂ and CS₂ to produce nickel bicarbonate (PN³P)Ni(OCOOH) (5) and bimetallic dithiocarbonate [(PN³P)NiS]₂CO (6) respectively, as well as to promote aryl isocyanate and isothiocyanate insertion into the Ni-OH bond to give the corresponding (PN³P)NiEC(O)NHAr complexes (E = O, 7; E = S, 8). In addition, 3 catalyzes the nitrile hydration to various amides with well-defined intermediates (PN³P)Ni-NHC(O)R (R = Me, 9; R = Ph, 10).

Full text of DOI:10.1039/c8dt03403f

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1
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Volume 45 Number
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January 2016 Pages 1–398
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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
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Monomeric nickel hydroxide stabilized by a sterically demanding
3
phosphorus-nitrogen PN P-pincer ligand: synthesis, reactivity and
catalysis
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a
DOI: 10.1039/x0xx00000x
Changguang Yao, Priyanka Chakraborty, Emanuele Aresu, Huaifeng Li, Chao Guan, Chunhui
a
b,c
a
Zhou, Lan-Chang Liang* and Kuo-Wei Huang*
www.rsc.org/
3
nd
3
Terminal nickel hydroxide complex (PN P)Ni(OH) (3) bearing the 2 generation phosphorus-nitrogen PN P-pincer ligand
has been synthesized and structurally characterized. As a nucleophile, 3 reacts with CO to afford the hydroxycarbonyl
3
3
complex 4, (PN P)Ni(COOH). 3 can also activate CO
2
and CS
2
to produce nickel bicarbonate (PN P)Ni(OCOOH) (5) and
3
bimetallic dithiocarbonate [(PN P)NiS]
2
CO (6) respectively, as well as to promote aryl isocyanate and isothiocyanate
3
insertion into the Ni-OH bond to give the corresponding (PN P)NiEC(O)NHAr complexes (E = O, 7; E= S, 8). In addition, 3
3
catalyzes the nitrile hydration to various amides with well-defined intermediates (PN P)Ni-NHC(O)R (R = Me,9, R = Ph,
1
0).
2
using (PCP)Ni-OH as the catalyst. Recently, Wendt and co-
5
Introduction
workers demonstrated the reactivities towards CO/CO of two
2
nickel hydroxides supported by POCsp3OP and PCN ligands,
2
respectively.
Late transition-metal (LTM) hydroxide complexes are some of
the most captivating intermediates involved in biological and
9, 31
1
-4
5, 6
Over recent years, pincer ligands have been extensively
recognized for their strong coordination capacity to stabilize
catalytic processes, such as the Wacker reaction. Different
from their group 4−6 inert counterparts, LTM hydroxides are
very exiguous and reactive due to the inherent weakness of
3
2-39
various metals.
We have been particularly interested in the
1
, 3, 7-9
exploration of the metal–ligand cooperative catalysis utilizing a
3
new class of pyridine-based phosphorus-nitrogen PN -pincer
their M-OH bond.
Over past decades, LTM hydroxide
complexes have emerged as the important synthons for
preparing new metal compounds; however, the thermal
complexes through deprotonation and reprotonation of one of
4
0-42
1
0-12
the NH arms.
4
Very importantly, in contrast to their CH
2
instability makes their synthesis very challenging.
Up to
3-45
analogs, we have demonstarted that the small change of
4
3-18 the arm has led to distinct catalytic reactvities
now several monomeric palladium and platinum hydroxides
1
have been isolated and structurally characterized,
6-53
and
5
4-56
different thermodynamic and kinetic properties.
however, their nickel analogs have less been explored despite
1
their higher oxophilicity.
3
9-31
19
Campora et al. and Hazari et
Furthermore, we have very recently extended these PN P-
pincer systems to prepare a new series of second-generation
3
diimine-amido PN P pincer complexes using a ligand post-
2
al. reported the synthesis and reactivity of the terminal
tBu
PCP)Ni-OH and ( PCP)Ni-OH complexes, respectively; Holm
4
iPr
(
5
7-59
modification strategy.
Herein, we demonstrated that the
and co-workers synthesized and studied the reactions of an
Me2
- 26
)(OH)] . The Piers
exceptional stability shown by these new compounds allowed
us to synthesize the corresponding monomeric hydroxo nickel
complex for the investigation on its reactivity and catalysis.
anionic hydroxo nickel complex [Ni(pyN
2
group reported the selective hydration of nitriles to amides by
Results and discussion
3
Synthesis and characterization of complex (PN P)Ni(OH) (3)
3
Pincer complex (PN P)NiCl (
1) was first converted into Ni
triflate compound
2
in a high yield of 95% via a metathesis
reaction, followed by the reaction with sodium hydroxide to
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Scheme 2. Reaction of complex
respectively. The degassed C
3
with CO.
solution of 4 was further
6
D
6
exposed to the argon atmosphere for one week, no change
was detected in the NMR spectroscopy. This is different from
1
9
29
the reports by the groups of Cámpora and Wendt , where
2
2
the bridged dimeric µ-CO -κ C,O species was formed via
decarbonylation of two hydroxycarbonyl complexes or
decomposition to multiple products, respectively, suggesting
that the ligand plays a significant role in determining the
stability and reactivity.
Activation of CO
At room temperature, complex
CO to afford the bicarbonate complex (PN P)NiOCOOH (
2 2
and CS
3
underwent a fast insertion of
3
5
), as
2
Scheme 1. Synthesis of complex
3
via metathesis reactions.
. Thermal ellipsoids are
corroborated by NMR signals of the bicarbonate proton and
carbon at 12.70 and 161.46 ppm respectively, as well as the IR
-1 29, 65
Fig. 1 Molecular structure of complex
3
absorption bands at 1618 and 1345 cm .
An attempt to
displayed at 50 % probability level; hydrogen atoms are
omitted for clarity. Selected bond lengths [Å] and angles [°]:
Ni(1)-N(1) 1.9056(19), Ni(1)-P(1) 2.1835(9), Ni(1)-P(2)
isolate this bicarbonate complex by removing the volatiles
66
under reduced pressure led to a complete deinsertion of CO2
to regenerate hydroxide 3. Again in contrast to the complexes
2
.1795(9), Ni(1)-O(1) 1.930(2), O(1)-H(100) 0.860(9); N(1)-
Ni(1)-O(1) 177.88(9), P(1)-Ni(1)-P(2) 165.97(3), P(1)-Ni(1)-O(1)
7.66(6), P(2)-Ni(1)-O(1) 96.37(6), Ni(1)-O(1)-H(100) 111.3(14).
9
quantitatively produce the target nickel hydroxide complex
3
(Scheme 1). After 12 h at 50 °C, it was observed that the
phosphorus resonance of
2 (δ 109.43 ppm) completely
disappeared with the appearance of a new signal at δ 98.85
ppm, indicative of the formation of a new species. The
presence of a Ni-OH fragment was confirmed by its
1
characteristic resonance at δ -3.73 ppm in H NMR spectrum,
consistent with those of Ni-OH groups previously reported in
2
6, 29, 31, 60, 61
literature.
connectivity in
To unambiguously establish the atom Scheme 3. Activation of CO and CS using complex 3.
2 2
3, single crystals suitable for X-ray diffraction
analysis were grown from a concentrated pentane solution at
room temperature. The Ni-O bond length of 1.930(2) Å shows
a covalent bond between the nickel and the oxygen atom; the
N1–Ni1–O1 angle of 177.88° exhibits that these three atoms
are almost in a straight line (Fig. 1).
Reaction of 3 with CO
LTM hydroxide complexes are known to serve as precursors
2
4, 26, 62-64
for preparing various metal compounds.
complex in hand, we set out to explore its reactivity in
relation to its nucleophilic character. Treatment of the
degassed C solution of with CO under the atmospheric
With
3
6
D
6
3
pressure and room temperature resulted in a color change
from red to colorless and formation of a hydroxycarbonyl
complex 4, proved by NMR spectroscopy and element analysis
Fig. 2 Molecular structure of complex 6. Thermal ellipsoids are
displayed at 50% probability level; hydrogen atoms are
omitted for clarity. Selected bond lengths [Å] and angles
[°]:Ni(1)-N(1) 1.912(2), Ni(1)-P(1) 2.2026(9), Ni(1)-P(2)
2.2201(10), Ni(1)-S(1) 2.2180(13), S(1)-C(28) 1.7330(12), C(28)-
O(1A) 1.399(3), C(28)-S(2) 1.6059(12), S(2)-Ni(1A) 2.2727(13);
P(1)-Ni(1)-P(2) 165.21(3), P(1)-Ni(1)-S(1) 94.76(5), P(1)-Ni(1)-
S(2A) 94.23(4), P(2)-Ni(1)-S(1) 98.25(4), P(2)-Ni(1)-S(2A)
(
Scheme 2). Different from the recent report of Wendt’s
2
group , the acidic proton at 10.23 ppm in H NMR and an
9
1
1
3
apparent triplet peak at 209.02 ppm in C NMR corresponding
to the –COOH group were both found
Et
Et
Et
Et
Et
N
Et
N
99.97(4),
N(1)-Ni(1)-S(1)
159.72(8),
O(1A)-C(28)-S(1)
C6D6
1
17.18(15), S(1)-C(28)-S(2) 118.80(6).
+
CO
N
N
N
N
r.t., 4h
(tBu)2P
t
(tBu)2P
t
Ni
P( Bu)2
Ni
P( Bu)2
OH
O
OH
3
4
2
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Scheme 4. Reactions of 3 and isocyanate/isothiocyanate.
iPr
(
PCP)NiOCOOH and (POCsp3OP)NiOCOOH obtained by
6
5
29
Cámpora and Wendt , our bicarbonate complex cannot be
further converted into a binuclear carbonate compound, in
2
3, 67
accordance with Holm’s reversible process.
This reversible insertion process intrigued us to explore the
reactivity of 3 and CS , a surrogate for CO . Upon addition of excess
CS to the C D solution of 3 and keeping the resultant solution at
2
2
2
6 6
3
1
room temperature for 2 h, the monitored P NMR spectrum
showed a new signal at 104.36 ppm, and no OH resonance was
1
detected in H NMR spectrum, indicating a new species formed.
Interestingly, a new carbon signal with an apparent quintet peak (J
1
3
=
4.1 Hz) was observed at 194.89 ppm in C NMR spectrum,
consistent with the CS insertion into the Ni-OH bond to produce a
2
C=O moiety located in a specific position with respect to four
-
1
phosphorus atoms. The presence of C=O vibration at 1670 cm in Fig. 3 Molecular structures of complexes
7 and 8. Thermal
+
ellipsoids are displayed at 50% probability level; hydrogen
atoms are omitted for clarity. Selected bond lengths [Å] and
the FTIR spectrum and the HRMS result of [M+1] (1169.54)
strongly support that the identity of complex 6 is a bimetallic
3
angles [°]: For complex
7
: Ni(1)-N(1) 1.8951(19), Ni(1)-P(1)
.2143(9), Ni(1)-P(2) 2.2080(8), Ni(1)-O(1) 1.861(2), O(1)-C(28)
.280(3), O(2)- C(28) 1.211(3), C(28)-N(4) 1.388(3); N(1)-Ni(1)-
complex with the formula C55
H
104
N
Ni
6 2
OP
4
S
2
of [(PN P)NiS]
2
CO,
2
1
consistent with the elemental analysis (see SI). The molecular
structure of 6 was unambiguously confirmed by the X-ray
3
O(1) 169.39(9), P(1)-Ni(1)-P(2) 165.47(3), P(1)-Ni(1)-O(1)
7.20(8), P(2)-Ni(1)-O(1) 97.22(8), Ni(1)-O(1)-C(28) 127.51(17).
For complex : Ni(1)-N(1) 1.907(3), Ni(1)-P(1) 2.2206(13),
Ni(1)-P(2) 2.2035(11), Ni(1)-S(1) 2.2168(12), S(1)-C(28)
.745(3), O(1)-C(28) 1.241(4), C(28)-N(4) 1.349(4); N(1)-Ni(1)-
S(1) 171.23(10), P(1)-Ni(1)-P(2) 164.71(4), P(1)-Ni(1)-S(1)
7.92(5), P(2)-Ni(1)-S(1) 97.32(5), Ni(1)-S(1)-C(28) 105.71(12).
diffraction analysis: two Ni fragments ([(PN P)Ni]) are connected by
9
the -SC(O)S- bridge (Fig. 2), a unique core structure unknown in the
8
6
8-70
literature.
2
Several reactions of metal hydroxides with CS have
been reported to exclusively give the hydrosulfido complexes
1
7
1-73
products or intermediates.
2
In those systems, CS initially inserts
into the M-OH bond to form the –SC(S)OH moiety followed by
extrusion of COS to yield hydrosulfido complexes in part driven by
the favorable formation of the M–S bond. However, in our case, no
Ni-SH formation was detected by NMR. Our observations suggest
9
of the bulky substituents. This kind of coordination manner is
7
comparable to Pérez’s rhenium complex but in contrast to
6
7
7
2
that once CS inserts into the Ni-OH bond, the proton of -SC(S)OH Esteruelas’s osmium compound which features a bidentate
intermediate can be rapidly deprotonated by another 3 to afford carbamato ligand. Three well-defined carbamato nickel
the bimetallic complex 6 with water as the by-product, presumably compounds have been reported in the literature, however, all
due to the strong basicity of 3.
of them are generated from the reaction of CO
2
insertion into
Compared to these square planar
nickel carbamates ([(POCsp3OP)NiOC(O)NHAr] (1.910 Å),
24, 74, 75
the Ni-NHR bond.
Reactions of 3 with isocyanate/isothiocyanate
iPr2
[
(
(
(PCP)Ni{OC(O)NH }] (1.925 Å) and (MeSiP )Ni(OC(O)NHAr)
2
The nucleophilic property of
3 was further examined with
1.948 Å)), complex
7 holds the shortest Ni-O bond distance
isocyanate and isothiocyanate as electrophiles. Hydroxide
3
1.861 Å). When 2,6-dimethylphenyl isothiocyanate as used,
reacts readily with 2,6-dimethylphenyl isocyanate via formal
3
an analogous product (PN P)NiSC(O)NHAr
obtained, presumably because sulfur’s soft property is
24, 74, 75 beneficial to a stronger Ni-S bond, in good agreement with the
(8) was also
addition of the O-H bond to the C=N double bond at room
3
temperature to generate (PN P)NiOC(O)NHAr species
7, with a
1 13
CONH- group confirmed by H and C NMR.
-
7
6
report of the Pérez group (Scheme 5).
Identification of species 7 as a carbamate is also supported by
X-ray diffraction (Fig. 3): the carbamato moiety coordinates to
Ni as a monodentate ligand, presumably due to the presence
Scheme 5. Proposed mechanism for the formation of 8 from 3.
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5.77(8), Ni(1)-N(4)-C(28) 127.6(2), N(4)-C(28)-O(1) 123.7(3),
N(4)-C(28)-C(29) 118.2(3), O(1)-C(28)-C(29) 118.1(3).
Nitriles hydration to amides catalyzed by 3
The formation of amides by hydration of nitriles using LTM
5, 78-81
hydroxides as catalysts has been reported in literature.
a
Table 1. Catalytic hydration of nitriles by using complex 3.
2
However, to the best of our knowledge, only Piers’
investigation refers to the isolable intermediate with the role
2
of the hydroxo compound (PCP)Ni-OH unconfirmed. This
5
prompted us to investigate the reaction of
(
3
Scheme 6). After heating the C D solution of 3 and excess
and nitriles
6
6
acetonitrile at 60 °C for 72 h in the absence of water, the
activation of acetonitrile was successfully achieved to form
3
PN P)NiNHC(O)Me (
(
9), a bound acetamide nickel complex, in
sharp contrast to Piers’ work where no reaction occurred
between benzonitrile and the hydroxo nickel complex without
a
Conditions (isolated yields): Complex
3 (20 µmol, 11.1 mg),
nitrile (2 mmol), distilled water (0.1 mL), THF (1 mL),
b
temperature (100 °C), Time (24 h). Time (72h).
water. The structure of
9 was again confirmed by X-ray
diffraction analysis (Fig. 4). The deprotonated acetamide
coordinates to the Ni center trans to the central N of the
pincer ligand. When the reaction of
out, the bound benzamide compound (PN P)NiNHC(O)Ph (10
was obtained. The molecular structure of 10 was also
identified crystallographically (Fig. 4). The reaction of with
O in THF at 100 °C regenerates and affords the
corresponding amide compounds, suggesting that it is the
intermediate for hydration of acetonitrile and hydroxide can
3 with PhCN was carried
3
Scheme 6. Reactions of
3
and nitriles.
)
9
H
2
3
3
play a role of catalyst. Our results serve as a clear evidence to
support that the catalytic cycle is completed by regeneration
of the hydroxo complex 3. The catalytic activity of 3 for the
nitrile hydration was thus further examined with a range of
nitriles including alkyl/aryl nitriles, unsaturated nitriles,
heteroatom-containing nitriles, etc. (Table 1). All the target
amides were successfully obtained in moderate to high yields.
As monitored by NMR, acrylonitrile was completely consumed,
but only 64% acrylamide was obtained, probably involving the
subsequent addition reaction of the resultant C=C double bond
2
5
with water at the high temperature. The low yields of 12c
Et
Fig. 4 Molecular structures of complexes
9
and 10. Thermal
Et
Et
ellipsoids are displayed at 50% probability level; hydrogen
atoms are omitted for clarity. Selected bond lengths [Å] and
O
N
N
N
(tBu)2P
t
Ni
P( Bu)2
R
NH2
Et
angles [°]: For complex
9
: Ni(1)-N(1) 1.905(4), Ni(1)-P(1)
OH
R-CN
(
3)
2.2186(12), Ni(1)-P(2) 2.1970(12), Ni(1)-N(4) 1.876(4), N(4)-
H2O
C(28) 1.318(6), C(28)-O(1) 1.242(7); N(1)-Ni(1)-N(4) 176.50(18),
P(1)-Ni(1)-P(2) 165.04(5), P(1)-Ni(1)-N(4) 99.07(12), P(2)-Ni(1)-
N(4) 95.86(12), Ni(1)-N(4)-C(28) 128.3(4), N(4)-C(28)-O(1)
Et
Et
Et
Et
Et
N
N
N
N
1
23.4(5), N(4)-C(28)-C(29) 117.8(5), O(1)-C(28)-C(29) 118.7(5).
P(tBu)2 Ni P(tBu)2
N
N
Ni
N
NH
O
(tBu)2P
P( Bu)2
t
For complex 10: Ni(1)-N(1) 1.903(2), Ni(1)-P(1) 2.2113(10),
Ni(1)-P(2) 2.2029(10), Ni(1)-N(4) 11.888(2), N(4)-C(28)
HO
R
1.309(4), C(28)-O(1) 1.241(4); N(1)-Ni(1)-N(4) 176.04(10), P(1)-
(II)
R
(I)
Ni(1)-P(2) 165.62(3), P(1)-Ni(1)-N(4) 98.55(7), P(2)-Ni(1)-N(4)
and 12f were presumably attributed to the competitive
coordination of the oxygen atoms
4
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diffraction data were collected using Bruker-AXS KAPPA-APEXII CCD
Scheme 7. A proposed catalytic mechanism for nitrile diffractometer.
hydration by complex
3
.
3
and amino groups with the nitrile nitrogen to the central Synthesis of complex 2, (PN P)Ni(OTf)
nickel. Nevertheless, the yields could be improved with a
AgOTf (308 mg, 1.2 mmol) was added to the toluene solution of
longer reaction time. Compared to Piers’ system, nickel
hydroxide ( ) displays a lower catalytic activity for nitrile
3
(
PN P)NiCl (1) (10 mL, 575 mg, 1.0 mmol). The resulting suspension
3
was stirred 24 h at 50 °C, filtered and all the volatiles were removed
hydration at 100 °C, probably due to the enhanced stability of
the bound amide intermediate, which was not observed in
in vacuo to yield a red solid (654 mg, 95.0 %). The elemental
1
analysis sample was crystallized from pentane. H NMR (500 MHz,
2
5
Piers’ study.
C
6
D
6
) δ = 5.25 (t, J = 3.4 Hz, 1H, -C(Et)=CH-), 2.38 (q, J = 7.4 Hz, 2H, -
CH ), 1.91 (dq, J = 14.7 Hz, 7.4 Hz, 2H, -CH CH ), 1.52 (dt, J = 18.3
Hz, 7.1 Hz, 36H, -PC(CH ), 1.17 (dq, J = 14.8 Hz, 7.4 Hz, 2H, -
Based on the synthetic cycle and hydration results, the
plausible catalytic mechanism was proposed (Scheme 7). The
hydroxide ligand undergoes the nucleophilic attack on the
CH
2
3
2
3
3 3
)
CH
2
2
CH
3
), 1.03 (t, J = 7.4 Hz, 3H, -CH
2
CH
3
), 0.59 (t, J = 7.4 Hz, 6H, -
(
presumably coordinated) nitrile substrate to form
intermediate , which then isomerizes to afford the bound
amide intermediate II. Finally, regeneration of nickel hydroxide
complex proceeds with the reaction of II and H O and
31
1
13
CH
CH
3
); P{ H} NMR (202 MHz, C
6
D
6
): δ 109.43 (s); C NMR (126
I
MHz, C
6 6
D ) δ = 182.32 (t, J = 4.9 Hz, -N=C-), 170.41 (t, J = 5.5 Hz, -
N=C-), 139.31 (s, -C(Et)=CH-), 135.37 (t, J = 8.5 Hz, -C(Et)=CH-),
3
2
1
18.83 (q, J = 318.9 Hz, -CF
9.9 Hz, -PC(CH ), 36.34 (s, -C(CH
), 28.18 (d, J = 2.7 Hz, -PC(CH
4.46 (s, -C(CH CH )=CH-), 9.79 (s, -C(CH
%) for C28 NiO
3
), 50.80 (t, J = 7.3 Hz, -C(Et)
CH ), 28.40 (d, J = 2.9 Hz, -
), 27.19 (s, -C(CH CH )=CH-),
CH ). Elemental analysis
2
), 38.48 (t, J
generates the amide product.
=
3
)
3
2
3 2
)
PC(CH
3
)
3
3
)
3
2
3
1
2
3
2
3 2
)
Conclusions
(
H
52
F
3
N
3
3
P
2
S: Calc. C, 48.85; H, 7.61; N, 6.10. Found: C,
In summary, we have synthesized a new monomeric Ni-OH 48.72; H, 7.80; N, 5.93.
complex ( ) via a metathesis reaction of its triflate precursor
3
3
with NaOH, and demonstrated its diverse reactivity in respect Synthesis of complex 3, (PN P)Ni(OH)
of its nucleophilic character.
give a hydroxycarbonyl complex
reversibly CO to form a nickel bicarbonate compound
activate CS to generate the unprecedented binuclear
dithiocarbonate complex [(PN P)NiS] CO (6). Moreover, aryl
3
can react with CO at 1 atm to
. It is able to activate
, and
NaOH (48 mg, 1.2 mmol) was added to the toluene solution of
4
3
(
PN P)NiOTf (2) (10 mL, 688 mg, 1.0 mmol). The resulting
2
5
suspension was stirred 12 h at 50 °C, filtered and all the volatiles
2
were removed in vacuo to yield a red solid (550 mg, 99.0 %). The
3
2
sample suitable for X-ray diffraction analysis was crystallized from
isocyanate and isothiocyanate undergo the insertion into the
3
Ni-OH bond to afford corresponding (PN P)Ni-EC(O)NHAr (E =
1
concentrated pentane. H NMR (500 MHz, C
6
D
6
) δ = 5.39 (t, J = 3.3
CH ), 2.11 (dq, J =
), 1.54 (ddd, J = 11.1 Hz, 9.1 Hz, 2.4 Hz,
), 1.29 (dq, J = 14.9 Hz, 7.5 Hz, 2H, -CH CH ), 1.16 (t, J
7.4 Hz, 3H, -CH CH ), 0.71 (t, J = 7.4 Hz, 6H, -CH CH ), -3.73 (t, J =
): δ 98.85 (d, J = 301.2
) δ = 181.84
dd, J = 9.3 Hz, 4.2 Hz, -N=C-), 170.29 (dd, J = 9.2 Hz, 5.0 Hz, -N=C-),
Hz, 1H, -C(Et)=CH-), 2.55 (q, J = 7.4 Hz, 2H, -CH
2
3
O, S) compounds.
3 also serves as a catalyst for the hydration
3
1
3
=
6
4.7 Hz, 7.4 Hz, 2H, -CH
6H, -PC(CH
2 3
CH
of nitriles to amides with the well-defined (PN P)Ni-NHC(O)R
intermediates.
3
)
3
2
3
2
3
3
1
2
3
1
6 6
.2 Hz, 1H, -OH); P{ H}NMR (202 MHz, C D
13
6 6
Hz), 98.35 (d, J = 301.2 Hz); C NMR (126 MHz, C D
Experimental section
(
General procedures
1
38.89 (s, -C(Et)=CH-), 135.85 (dd, J = 9.2 Hz, 5.0 Hz, -C(Et)=CH-),
), 36.80 (td, J = 14.7 Hz, 14.3 Hz,
CH ), 28.21 (dd, J = 29.2 Hz, 4.3
)=CH-), 14.81 (s, -C(CH CH )=CH-),
). Elemental analysis (%) for C27
All experiments (if not mentioned otherwise) with metal 49.91 (dd, J = 12.0 Hz, 2.6 Hz, -C(Et)
complexes were carried out under an atmosphere of dry argon in a 6.4 Hz, -PC(CH ), 36.22 (s, -C(CH
glovebox or using standard Schlenk techniques. All glassware was Hz, -PC(CH ), 27.13 (s, -C(CH CH
rigorously dried. All solvents were distilled from sodium 9.89 (s, -C(CH CH
2
3
)
3
2
3 2
)
3
)
3
2
3
2
3
2
3
)
2
H
53
N
3
P
2
ONi: Calc.
benzophenone ketyl prior to use. All other chemicals were C, 58.29; H, 9.60; N, 7.55. Found: C, 58.46; H, 9.68; N, 7.62.
commercially available and used as received. Complex 1 was
5
7
3
prepared according to the literature procedure . NMR spectra Synthesis of complex 4, (PN P)Ni(COOH)
1
13
31
were recorded at 400 MHz ( H), 101 MHz ( C), and 162 MHz ( P)
A solution of complex 3 (11.1 mg, 20.0 µmol in C
6
D
6
) was put in a J-
1
using a Bruker Avance-400 NMR spectrometer, 500 MHz ( H), 126
Young NMR tube. The tube was connected to Schlenk line and then
degassed and saturated with CO three times. The color of the
solution changed to colorless and completion of the reaction after 4
1
3
31
MHz ( C), and 202 MHz ( P) using a Bruker Avance-500 NMR
1
13
31
spectrometer, and 600 MHz ( H), 152 MHz ( C), and 243 MHz ( P)
using a Bruker Avance-600 NMR spectrometer. All spectra were
hours. The resultant C
6
D
6
solution was directly used for analysis in
NMR experiments. H NMR (500 MHz, C ) δ = 10.23 (br, 1H, -
COOH), 5.50 (t, J = 3.1 Hz, 1H, -C(Et)=CH-), 2.61 (q, J = 7.4 Hz, 2H, -
CH CH ), 2.16 (dq, J = 12.7 Hz, 7.4 Hz, 2H, -CH CH ), 1.56–1.43 (m,
6H, -PC(CH ), 1.36 (dq, J = 12.8 Hz, 7.4 Hz, 2H, -CH CH ), 1.20 (t, J
7.4 Hz, 3H, -CH CH ), 0.74 (t, J = 7.4 Hz, 6H, -CH CH
) δ = 114.63 (d, J = 194.2 Hz), 112.92 (d, J = 194.2 Hz);
1
recorded at 25 °C. H NMR chemical shifts were referenced to the
1
6 6
D
residual hydrogen signals of the deuterated solvents (7.16 ppm,
1
3
13
C
6
D
6
), and the C NMR chemical shifts were referenced to the
C
2
3
2
3
signals of the deuterated solvents (128.06 ppm, C ). Elemental
6 6
D
3
=
3
)
3
2
3
31
analyses were carried out on a Flash 2000 elemental analyzer.
HRMS data were recorded on a Finnigan MAT 95 system. The X-ray
1
2
3
2
3
); P{ H} (202
13
MHz, C
6
D
6
C
This journal is © The Royal Society of Chemistry 2018
Dalton Trans., 2018, 00, 1-9 | 5
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Dalton Transactions
Page 6 of 9
View Article Online
DOI: 10.1039/C8DT03403F
ARTICLE
Dalton Transactions
NMR (126 MHz, , C
6
D
6
) δ = 209.93–208.34 (m, -COOH), 184.48 (s, A solution of 3 (11.1 mg, 20.0 µmol) and 2,6-dimethylphenyl
(0.6 mL) was put in a J-Young
, 139.35 (s, -C(Et)=CH-), 136.07 (d, J = 16.3 Hz, -C(Et)=CH-), 49.87 (d, NMR tube. The red solution was stirred for 4 hours at room
6 6
excess CO), 180.10 (d, J = 9.2 Hz, -N=C-), 168.71 (d, J = 9.7 Hz, -N=C- isocyanate (2.9 mg, 20.0 µmol) in C D
)
3
1
J = 13.8 Hz, -C(Et)
2
), 37.88 (ddd, J = 19.6 Hz, 11.7 Hz, 4.4 Hz, - temperature, completion of the reaction was confirmed by P NMR
), 36.22 (s, -C(CH CH ), 28.35 (dd, J = 24.1 Hz, 4.2 Hz, - spectroscopy. Removal of volatiles in vacuo resulted in a red solid
), 27.02 (s, -C(CH CH )=CH-), 14.80 (s, -C(CH CH )=CH-), 9.94 that was used for analysis in NMR experiments (13.6 mg, 97.0 %).
CH ). The sample suitable for elemental analysis was Crystals suitable for X-ray diffraction were grown by slow
crystallized from concentrated pentane. Elemental analysis (%) for evaporation of a pentane solution. H NMR (500 MHz, C
Ni: Calc. C, 57.55; H, 9.14; N, 7.19. Found: C, 57.74; H, 7.04 (d, J = 7.4 Hz, 2H, Ph-H), 6.97 (dd, J = 8.3 Hz, 6.5 Hz, 1H, Ph-H),
.23; N, 7.08. 5.45 (s, 1H, -CONH-), 5.36 (t, J = 3.2 Hz, 1H, -C(Et)=CH-), 2.51 (q, J =
.3 Hz, 2H, -CH CH ), 2.33 (s, 6H, -PhCH ), 2.07 (dq, J = 14.7 Hz, 7.4
Hz, 2H, -CH CH ), 1.58 (ddd, J = 17.9 Hz, 9.6 Hz, 4.2 Hz, 36H, -
PC(CH
PC(CH
3
3
)
)
3
3
2
3 2
)
2
3
2
3
(
s, -C(CH
2
3 2
)
1
6 6
D ) δ =
28 53 3 2 2
C H N P O
9
7
2
3
3
3
2
3
Synthesis of complex 5, (PN P)Ni(OCOOH)
PC(CH
Hz, 3H, -CH
MHz, C ): δ 103.31 (d, J = 280.8 Hz), 103.16 (d, J = 280.8 Hz);
NMR (126 MHz, C ) δ = 181.66 (dd, J = 7.8 Hz, 4.2 Hz, -N=C-),
70.06 dd, J = 7.5 Hz, 5.5 Hz, -N=C-), 157.30 (s, -CONH-), 138.65 (s, -
3
)
3
), 1.26 (dq, J = 14.8 Hz, 7.4 Hz, 2H, -CH
2 3
CH ), 1.13 (t, J = 7.4
A solution of complex 3 (11.1 mg, 20.0 µmol in C
6
D
6
) was put in a J-
31
1
2
CH ), 0.71 (t, J=7.4 Hz, 6H, -CH CH ); P{ H}NMR (202
3
2
3
Young NMR tube. The tube was connected to Schlenk line and then
degassed and saturated with CO three times. The color of the
solution changed to yellow and completion of the reaction
immediately. The resultant C solution was directly used for
analysis in NMR experiments. H NMR (400 MHz, C ) δ = 12.70
br, 1H, -NiOCOOH), 5.35 (t, J = 3.3 Hz, 1H, -C(Et)=CH-), 2.47 (qd, J =
.3 Hz, 1.0 Hz, 2H, -CH CH ), 2.03 (dq, J = 12.8 Hz, 7.4 Hz, 2H, -
CH CH ), 1.56 (ddd, J = 12.0 Hz, 9.4 Hz, 4.3 Hz, 36H, -PC(CH ), 1.24
dq, J = 12.8 Hz, 7.4 Hz, 2H, -CH CH ), 1.10 (t, J = 7.4 Hz, 3H, -
CH CH ), 0.67 (t, J = 7.4 Hz, 6H, -CH CH
): δ 104.19 (d, J = 273.8 Hz), 104.04 (d, J = 273.8 Hz); C NMR
151 MHz, C ) δ = 182.15 (s, -N=C-), 170.48 (t, J = 6.4 Hz, -N=C-),
61.46 (s, Ni-OCOOH), 139.09 (s, -C(Et)=CH-), 138.19–133.79 (m, -
C(Et)=CH-), 124.77 (excess CO ), 52.68–45.12 (m, -C(Et) ), 37.42 (td,
J = 11.8 Hz, 6.9 Hz, -PC(CH ), 36.36 (s, -C(CH CH ), 28.05 (dd, J =
5.3 Hz, 3.6 Hz, -PC(CH ), 27.17 (s, -C(CH CH )=CH-), 14.62 (s, -
13
6
D
6
C
2
6 6
D
1
6 6
D
1
C(Et)=CH-), 138.04 (s, Ph-C), 135.37 (dd, J = 12.0 Hz, 4.9 Hz, -
C(Et)=CH-), 134.31(s, Ph-C), 124.74(s, Ph-C), 49.85 (dd, J = 10.4 Hz,
6 6
D
(
4
.3 Hz, -C(Et)
2
), 37.03 (dt, J = 12.3 Hz, 7.9 Hz, -PC(CH
), 27.72 (dt, J = 20.8 Hz, 2.7 Hz, -PC(CH
)=CH-), 19.22 (s, PhCH ), 14.30 (s, -C(CH CH
). Elemental analysis (%) for C36 NiO
1.46; H, 8.88; N, 7.96. Found: C, 61.38; H, 8.95; N, 8.02. HRMS (ESI)
3
)
3
), 36.01 (s, -
), 26.83 (s, -
)=CH-), 9.52 (s,
: Calc. C,
7
2
3
C(CH
C(CH
2
2
CH
CH
3
3
)
2
3 3
)
2
3
3 3
)
3
2
3
(
2
3
-
C(CH
2
CH
3
)
2
H
62
N
4
2 2
P
3
1
1
2
3
2
3
). P{ H} NMR (162 MHz,
6
13
C
6
D
6
+
Calcd. for C36
03.3772.
62 4 2 2
H N NiO P : requires [M+H] 703.3780, Found:
(
6 6
D
7
1
3
2
2
Synthesis of complex 8, (PN P)Ni(SCONHC
A solution of 3 (11.1 mg, 20.0 µmol) and 2,6-dimethylphenyl
isothiocyanate (3.3 mg, 20.0 µmol) in C (0.6 mL) was put in a J-
Young NMR tube. The red solution was stirred for 4 hours at room
6 3 2
H -2,6-Me )
3
)
3
2
3 2
)
2
3
)
3
2
3
6 6
D
C(CH
2
CH
3
2 3 2
)=CH-), 9.81 (s, -C(CH CH ) ).
3
1
3
temperature, completion of the reaction was confirmed by P NMR
spectroscopy. Removal of volatiles in vacuo resulted in a red solid
that was used for analysis in NMR experiments (13.9 mg, 96.5 %).
Synthesis of complex 6, [(PN P)NiS]CO
A solution of 3 (11.1 mg, 20.0 µmol) and carbon disulfide (7.6 mg,
00.0 µmol) in C (0.6 mL) was put in a J-Young NMR tube. The
red solution was kept at room temperature for 2 hours, completion
1
6 6
D
Crystals suitable for X-ray diffraction were grown by slow
1
evaporation of a pentane solution. H NMR (500 MHz, C
6
D
6
) δ =
3
1
of the reaction was confirmed by P NMR spectroscopy. Removal
of volatiles in vacuo resulted in a dark red solid that was used for
analysis in NMR experiments (11.2 mg, 95.9 %). Crystals suitable for
6
.97 (m, 3H, Ph-H), 6.72 (s, 1H, -CONHAr), 5.43 (t, J = 3.3 Hz, 1H, -
C(Et)=CH-), 2.56 (q, J = 7.4 Hz, 2H, -CH CH ), 2.32 (s, 6H, -PhCH ),
.11 (dq, J = 12.8 Hz, 7.4 Hz, 2H, -CH CH ), 1.61 (ddd, J = 13.6 Hz, 9.3
Hz, 4.2 Hz, 36H, -PC(CH ), 1.31 (dq, J = 12.8 Hz, 7.5 Hz, 2H, -
), 1.16 (t, J = 7.4 Hz, 3H, -CH CH ), 0.73 (t, J=7.4 Hz, 6H, -
): δ 103.05 (d, J = 290.9 Hz),
) δ = 180.89 (dd, J
7.8 Hz, 4.0 Hz, -N=C-), 170.35 (s, -CONH-), 169.49 (t, J = 6.4 Hz, -
2
3
3
2
2
3
X-ray diffraction were grown by slow evaporation of a THF solution.
3 3
)
1
H NMR (600 MHz, C
qd, J = 7.4 Hz, 1.1 Hz, 2H, -CH
CH CH ), 1.63 (ddd, J = 20.0 Hz, 9.6 Hz, 4.0 Hz, 36H, -PC(CH
dq, J = 12.8 Hz, 7.4 Hz, 2H, -CH
CH ), 0.74 (t, J = 7.4 Hz, 6H, -CH
6
D
6
) δ = 5.44 (t, J = 3.2 Hz, 1H, -C(Et)=CH-), 2.58
CH ), 2.13 (dq, J = 12.8 Hz, 7.3 Hz, 2H,
), 1.33
), 1.17 (t, J = 7.4 Hz, 3H, -
CH
2
2
CH
3
2
3
(
-
(
2
3
31
1
CH
CH
3
); P{ H}NMR (202 MHz, C
6
D
6
3
)
3
13
2
3
1
=
6 6
02.90 (d, J = 290.9 Hz); C NMR (126 MHz, C D
2
CH
3
31
1
CH
2
3
2
CH
3
); P{ H}NMR (243 MHz,
N=C-), 139.00 (s, -C(Et)=CH-), 137.10 (s, Ph-C), 135.87 (dd, J = 12.0
Hz, 4.8 Hz, -C(Et)=CH-), 135.33 (s, Ph-C), 126.25 (s, Ph-C), 50.32 (dd,
1
3
C
6
D
6
): δ 104.36 (d, J = 281.9 Hz), 104.24 (d, J = 281.9 Hz); C NMR
126 MHz, C ) δ = 194.89 (q, J = 4.1 Hz, -SCO-), 180.21 (dd, J = 7.3
Hz, 4.1 Hz, -N=C-), 169.17–168.92 (m, -N=C-), 138.72 (s, -C(Et)=CH-),
35.94 (dd, J = 11.4 Hz, 5.3 Hz, -C(Et)=CH-), 50.24 (dd, J = 9.7 Hz, 4.6
Hz, -C(Et) ), 38.49 (td, J = 11.2 Hz, 7.9 Hz, -PC(CH ), 36.43 (s, -
), 29.06 (d, J = 19.9 Hz, -PC(CH ), 27.29 (s, -
)=CH-), 9.99 (s, -C(CH CH ).
OP : Calc. C, 56.42; H, 8.95;
(
6 6
D
J = 10.0 Hz, 4.4 Hz, -C(Et)
2
), 38.64 (dt, J = 13.1 Hz, 9.6 Hz, -PC(CH
), 28.77 (dt, J = 21.0 Hz, 2.4 Hz, -PC(CH
CH )=CH-), 19.03 (s, PhCH
)=CH-), 9.96 (s, -C(CH CH
NiO : Calc. C, 60.09; H, 8.68; N, 7.79. Found: C, 60.06; H,
.70; N, 7.71. HRMS (ESI) Calcd. for C36 NiOP S: requires
3
)
3
),
),
-
3
2
6.47 (s, -C(CH
7.34 (s, -C(CH
CH
2 3 2
CH )
3
)
3
1
2
3
3
), 14.73 (s,
2
3 3
)
C(CH
2
3
2
3 2
) ). Elemental analysis (%) for
C(CH
C(CH
2
2
CH
CH
3
)
2
3 3
)
C
8
36
H
62
N
4
2 2
P
3
)=CH-), 14.74 (s, -C(CH
2
CH
3
2
3 2
)
H
62
N
4
2
Elemental analysis (%) for C55
H
104
N
Ni
6 2
4
S
2
+
[
M+H] 719.3551, Found: 719.3524.
N, 7.18. Found: C, 56.65; H, 8.63; N, 7.09. HRMS (APCI) Calcd. for
+
55
C H
104
N
6
Ni
2
4
OP S
2
: requires [M+H] 1169.5449, Found: 1169.5443.
3
Synthesis of complex 9, (PN P)Ni(NHCOMe)
3
Synthesis of complex 7, (PN P)Ni(OCONHC
6
H
3
-2,6-Me
2
)
6
| Dalton Trans., 2018, 00, 1-9
This journal is © The Royal Society of Chemistry 2018
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Page 7 of 9
Plea sDe a dl t oo nn oT tr aa nd sj ua cs tt i om nasrgins
View Article Online
DOI: 10.1039/C8DT03403F
Dalton Transactions
ARTICLE
1
A solution of 3 (11.1 mg, 20.0 µmol) and acetonitrile (4.0 mg, 100.0 Acrylamide (isolated yield, 64%): H NMR (400 MHz, DMSO-d
µmol) in C (0.6 mL) was put in a J-Young NMR tube. The red 7.51 (s, 1H), 7.07 (s, 1H), 6.18 (dd, J = 17.2 Hz, 10.0 Hz, 1H), 6.06
solution was heated for 72 hours at 60 °C, completion of the (dd, J = 17.2 Hz, 2.3 Hz, 1H), 5.59 (dd, J = 10.0 Hz, 2.3 Hz, 1H).
6
) δ =
6 6
D
1
3
C
3
1
reaction was confirmed by P NMR spectroscopy. Removal of NMR (101 MHz, DMSO-d
volatiles in vacuo resulted in a red solid that was used for analysis in 1,3-Benzodioxole-5-acetamide (isolated yield, 42%): H NMR (400
NMR experiments (11.7 mg, 98.2 %). Crystals suitable for X-ray MHz, DMSO-d ) δ = 7.38 (s, 1H), 6.90–6.77 (m, 3H), 6.70 (dd, J = 8.0
diffraction were grown by slow evaporation of a pentane solution at Hz, 1.7 Hz, 1H), 5.96 (s, 2H), 3.27 (s, 2H); C NMR (101 MHz, DMSO-
6
) δ = 166.35, 132.01, 125.51.
1
6
1
3
1
room temperature. H NMR (500 MHz, C
H, -C(Et)=CH-), 2.53 (q, J = 7.4 Hz, 2H, -CH
Hz, 7.4 Hz, 2H, -CH CH ), 1.90 (s, 3H, Ni-NHCOCH
6.9 Hz, 9.7 Hz, 3.8 Hz, 36H, -PC(CH ), 1.39–1.21 (m, 2H, -CH
.14 (t, J = 7.4 Hz, 3H, -CH CH ), 0.94 (s, 1H, Ni-NHC(O)CH ), 0.71 (t, Hz, 2H), 7.37 (s, 1H). C NMR (126 MHz, DMSO-d
): δ 103.61 (d, J 134.26, 131.22, 128.21, 127.46.
) δ = Nicotinamide (isolated yield, > 99%): H NMR (400 MHz, DMSO-d
81.35 (dd, J = 7.9 Hz, 4.2 Hz, -N=C-), 175.26 (s, -CONH-), 169.93 δ = 9.04 (dd, J = 2.3 Hz, 0.9 Hz, 1H), 8.69 (dd, J = 4.8 Hz, 1.7, 1H),
6
D
6
) δ = 5.41 (t, J = 3.2 Hz,
CH ), 2.08 (dq, J = 14.6 100.71, 41.84.
), 1.49 (ddd, J = Benzamide (isolated yield, 97%): H NMR (500 MHz, DMSO-d
CH ), 7.98 (s, 1H), 7.93–7.83 (m, 2H), 7.56–7.49 (m, 1H), 7.44 (t, J = 7.6
6
d ) δ = 172.37, 147.02, 145.69, 130.15, 122.01, 109.50, 107.94,
1
2
3
1
2
3
3
6
) δ =
1
3
)
3
2
3
1
3
1
2
1
3
3
6
) δ = 167.93,
3
1
2 3 6 6
J = 7.4 Hz, 6H, -CH CH ). P{ H}NMR (202 MHz, C D
1
3
1
=
1
292.9 Hz), 103.41 (d, J = 292.9 Hz); C NMR (101 MHz, C
6
D
6
6
)
(
dd, J = 8.0 Hz, 5.4 Hz, -N=C-), 138.99 (s, -C(Et)=CH-), 135.85 (dd, J = 8.29–8.11 (m, 2H), 7.62 (s, 1H), 7.48 (ddd, J = 7.9 Hz, 4.8 Hz, 0.9 Hz,
1
3
1
3
2
2
2.5 Hz, 4.4 Hz, -C(Et)=CH-), 50.06 (dd, J = 10.8 Hz, 3.9 Hz, -C(Et)
7.44 (dt, J = 12.6 Hz, 8.4 Hz, -PC(CH ), 36.34 (s, -C(CH CH
8.29 (dt, J = 20.2 Hz, 2.7 Hz, -PC(CH ), 27.18 (s, -C(CH CH
6.70 (s, CH C(O)NH-Ni), 14.70 (s, -C(CH CH )=CH-), 9.89 (s, - DMSO-d
CH ). Elemental analysis (%) for C29 NiOP : Calc. C, Hz, 2.0 Hz, 1H), 6.70 (s, 1H), 6.45 (d, J = 8.0 Hz, 1H), 4.93 (s, 2H),
8.30; H, 9.45; N, 9.38. Found: C, 58.39; H, 9.55; N, 9.38. HRMS (ESI) 4.49 (s, 2H). C NMR (101 MHz, DMSO-d
2
), 1H). C NMR (101 MHz, DMSO-d
6
) δ = 166.58, 151.94, 148.73,
3
)
3
2
3
)
2
), 135.22, 129.72, 123.45.
1
3
)
3
2
3
)=CH-), 3,4-Diaminobenzamide (isolated yield, 74%): H NMR (400 MHz,
3
2
3
6
) δ = 7.37 (s, 1H), 7.06 (d, J = 2.0 Hz, 1H), 6.98 (dd, J = 8.0
C(CH
2
3
)
2
H
56
N
4
2
13
5
6
) δ = 168.74, 138.49,
+
Calcd. for C29
97.3346.
H
56
N
4
NiOP
2
: requires [M+H] 597.3361, Found: 133.74, 122.65, 117.72, 114.20, 112.70.
5
3
Conflicts of interest
Synthesis of complex 10, (PN P)Ni(NHCOPh)
There are no conflicts to declare.
The procedure is similar to that of complex 11 with a yield of 97.7
1
%. H NMR (500 MHz, C
6
D
6
) δ = 8.03–7.92 (m, 2H, Ph-H), 7.19 (t, J =
7
.7 Hz, 2H, Ph-H), 7.10 (td, J = 7.1 Hz, 1.4 Hz, 1H, Ph-H), 5.43 (t, J =
.2 Hz, 1H, -C(Et)=CH-), 2.55 (q, J = 7.4 Hz, 2H, -CH CH ), 2.29 (s, 1H,
CH ), 1.50 (ddd,
), 1.31 (dq, J = 12.8 Hz, 7.4
), 1.15 (t, J = 7.4 Hz, 3H, -CH CH ), 0.74 (t, J = 7.4 Hz,
): δ 104.46 (d, J = 288.8
Hz), 104.28 (d, J = 288.8 Hz); C NMR (126 MHz, C ) δ = 181.48
dd, J = 7.9 Hz, 4.1 Hz, -N=C-), 172.39 (s, -CONH-), 170.02 (dd, J = 8.1
Hz, 5.3 Hz, -N=C-), 140.37 (s, Ph-C), 139.04 (s, -C(Et)=CH-), 135.88 Notes and references
dd, J = 12.5 Hz, 4.5 Hz, , -C(Et)=CH-), 128.84 (s, Ph-C), 127.04 (s, Ph-
C), 50.14 (dd, J = 10.7 Hz, 3.9 Hz, -C(Et) ), 37.55 (dt, J = 12.5 Hz, 8.3
Hz, -PC(CH ), 36.38 (s, -C(CH CH
), 28.35 (dt, J = 21.0 Hz, 2.5 Hz, 1.
, 27.21 (s, -C(CH CH )=CH-), 14.71 (s, -C(CH CH )=CH-), 9.93 (s, -
C(CH CH ). Elemental analysis (%) for C34 NiOP : Calc. C,
1.92; H, 8.86; N, 8.50. Found: C, 62.13; H, 8.92; N, 8.39.
Acknowledgements
3
2
3
Ni-NHC(O)Ph), 2.10 (dq, J = 12.8 Hz, 7.4 Hz, 2H, -CH
J = 15.9 Hz, 9.7 Hz, 3.8 Hz, 36H, -PC(CH
Hz, 2H, -CH CH
H, -CH CH
2
3
We acknowledge the financial supports from King Abdullah
University of Science and Technology (KAUST) and from the
Ministry of Science and Technology of Taiwan (MOST 106-
3 3
)
2
3
2
3
3
1
1
6
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3 6 6
). P{ H}NMR (202 MHz, C D
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6 6
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Acetamide (isolated yield, > 99%): H NMR (500 MHz, DMSO-d
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