Synthesis, structure, computational and catalytic activities of palladium complexes containing hydrazide based amino-phosphine ligands

Article abstract of DOI:10.1016/j.jorganchem.2018.11.025

Two new N, N-bis(diphenylphosphino)-amine ligands [where amine = N-Aminophthalimide (in L₁) and Hydrazine dihydrochloride (in L₂)] and their Pd(II) complexes, C₁ and C₂ have been synthesized and characterized by IR and NMR spectroscopies. Single crystal X-ray diffraction techniques have been used to determine the crystal structures of the complexes. Moreover, the catalytic activities of mentioned complexes in Heck coupling reactions have been assessed. The NBO analysis has been used to investigate the nature of the metal-ligand interactions. In the case of L₂, preparation route could have produced two different products (Pro.1 and Pro.2), but only one structure has been gained which has been prepared in high purity. To address the reason for this manner, kinetics and thermodynamics of two different pathways that could have led to possible products have been investigated theoretically.

Full text of DOI:10.1016/j.jorganchem.2018.11.025

Accepted Manuscript
Synthesis, structure, computational and catalytic activities of palladium complexes
containing hydrazide based amino-phosphine ligands
Khodayar Gholivand, Mohammad Kahnouji, Yazdan Maghsoud, Mahdieh Hosseini,
Stephen Mark Roe
PII:
S0022-328X(18)30767-8
DOI:
https://doi.org/10.1016/j.jorganchem.2018.11.025
JOM 20645
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 31 August 2018
Revised Date: 19 October 2018
Accepted Date: 16 November 2018
Please cite this article as: K. Gholivand, M. Kahnouji, Y. Maghsoud, M. Hosseini, S. Mark Roe,
Synthesis, structure, computational and catalytic activities of palladium complexes containing
hydrazide based amino-phosphine ligands, Journal of Organometallic Chemistry (2018), doi: https://
doi.org/10.1016/j.jorganchem.2018.11.025.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Synthesis, Structure, Computational and Catalytic Activities of Palladium
Complexes Containing Hydrazide Based Amino-Phosphine Ligands
Khodayar Gholivand, Mohammad Kahnouji, Yazdan Maghsoud, Mahdieh Hosseini and Stephen Mark Roe

ACCEPTED MANUSCRIPT
Synthesis, Structure, Computational and Catalytic Activities of Palladium
Complexes Containing Hydrazide Based Amino-Phosphine Ligands
a, , †
a, †
a, †
a
Khodayar Gholivand, * Mohammad Kahnouji, Yazdan Maghsoud, Mahdieh Hosseini,
b
Stephen Mark Roe
a
Department of Chemistry, Faculty of Science, Tarbiat Modares University, Tehran, Iran.
b
Department of Chemistry, School of Life Sciences, University of Sussex, Brighton, BN19QJ, UK.
†
These authors contributed equally to this manuscript.
Abstract
Two new N, N-bis(diphenylphosphino)-amine ligands [where amine = N-Aminophthalimide (in
L ) and Hydrazine dihydrochloride (in L )] and their Pd(II) complexes, C and C have been
1
2
1
2
synthesized and characterized by IR and NMR spectroscopies. Single crystal X-ray diffraction
techniques have been used to determine the crystal structures of the complexes. Moreover, the
catalytic activities of mentioned complexes in Heck coupling reactions have been assessed. The
NBO analysis has been used to investigate the nature of the metal-ligand interactions. In the case
of L , preparation route could have produced two different products (Pro.1 and Pro.2), but only
2
one structure has been gained which has been prepared in high purity. To address the reason for
this manner, kinetics and thermodynamics of two different pathways which could have led to
possible products have been investigated theoretically.
Keywords: Amino-phosphines, Palladium complexes, Theoretical studies, Heck reaction.
1

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*
Corresponding author’s E-mail address: gholi_kh@modares.ac.ir
1
. Introduction
In recent years, some researchers have focused on the synthesis and characterization of new
[
1-6]
phosphorus (III) ligands for various applications such as metal-catalyzed reactions , because
of the stabilization of transition metals in low valence, especially with electron-rich transition
[
7-11]
metals
. Among different transition metals, rhodium, ruthenium, palladium and platinum
complexes containing phosphine ligands have shown high catalytic potential and have become
[
12-17]
the most popular organometallics used in organic synthesis
. Bis(diphenylphosphino)amines
with short-bite character recently have been considered in molecular chemistry because of the
diversity in their mono and bidentate coordination modes to metals[11]. In particular, these
complexes can be nominated as appropriate catalysts for reactions such as allylic alkylation,
[
18-
amination, hydrogenation of olefins, hydroformylation, and Suzuki-Heck coupling reactions
2
4]
.
In the past years, synthesis and coordination chemistry of bis(phosphino) amines, RN(PR ) ,
2
2
have received considerable attention because of exhibiting different coordination behaviors,
when the donor-acceptor properties have been altered by incorporating a substituent at the ligand
[
25-27]
backbone
. Preparative routes enable access to various structural modifications via simple P–
[
27-30]
N bond formation
. In comparison to P–C–P linkage, P–N–P skeletons possess a broad
versatility, and by small variations in substituents, remarkable changes in the P–N–P angle and
conformation around the P-centers occurs. Consequently, by altering in substituents, their
coordination behaviors and the structural properties can change significantly. This feature allows
[
31-36]
the synthesis of a wide range of new complexes with transition metals
.
2

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In our previous works, the catalytic activities of palladium complexes containing P^P and P^N
[
37, 38]
chelated ligands have been studied
. Results have attested that palladium complexes,
containing P^N chelated ligands have had high catalytic reactivity, which could be related to the
[
39, 40]
lability of Pd–N bond and it is easy breaking during the Heck reactions
. To improve and
extend this area, we have selected two new complexes of palladium with different substituents
on the P^P chelating ligand.
IR and NMR spectroscopies have been used to characterize both ligands (L
the structures of related complexes (C and C ) have been determined by X-ray crystallography.
Concerning with the synthesis of L (bis(diphenylphosphino)hydrazine), preparation method
1 2
and L ). Besides,
1
2
2
could have led to two different products, but surprisingly, only one structure has been gained.
Kinetics and thermodynamics of two possible pathways have been probed theoretically to
demonstrate and prove the reason for this subject. Furthermore, the nature of the interactions and
the Wiberg bond indices (WBIs) of our complexes have been investigated to predict and assess
their catalytic behavior in Heck coupling reaction. Eventually, C and C complexes have been
1
2
successfully used as a pre-catalyst in the Heck cross-coupling reactions.
2
. Results and discussion
2
.1. Synthesis of ligands and complexes
Two new N, N-bis(diphenylphosphino)-amine ligands, where amine = N-aminophthalimide (in
L ) and hydrazine dihydrochloride (in L ), were prepared via aminolysis of the corresponding
1
2
amine with two equivalents of Ph PCl in the presence of triethylamine in dichloromethane
2
solution at 0 °C (Scheme 1). L and L were isolated as white and air-stable solids in high yields
1
2
3

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2
(80% and 75%, respectively) under anaerobic conditions and their reaction with [Pd(COD)Cl ]
finally gave the corresponding Pd(II) complexes in high yields (ca. 90%).
1
Scheme 1. Synthesis of ligands L , L2, and related complexes.
2
In the case of N, N-bis(diphenylphosphino)hydrazine (L ), two pathways are probable which can
give Pro.1 and Pro.2 (Scheme 2). Pro.1 was acquired experimentally, which was proved by NMR
spectroscopy of free ligand and X-ray diffraction of complex C , consequently.
2
2
.2. Spectroscopic characterization
3
The NMR spectra of all compounds were recorded in a non-coordinating solvent, CDCl at room
1
temperature. H NMR spectra of L
1
and L
2
showed multiplet peaks for the aromatic H atoms in
the regions 7.49–7.72 and 7.32–7.47 ppm, respectively. The aromatic H atoms of the amine were
4

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3
1
at 7.87 for L
1
and 5.30 for L
2
. The P–{1H} NMR spectra of the ligands showed one singlet in
7
7.5 and 80.03 ppm for L and L , respectively, which is in compatible with PNP rather than
1
2
PNH structure.
Scheme 2. Two possible pathways which give Pro.1 and Pro.2.
2
.3. Crystal structures
Single crystals of C and C were obtained from a solution of dichloromethane by slow
1
2
evaporation at room temperature with good quality. Crystallographic data of mentioned
complexes as well as their geometric parameters are summarized in Tables 1 and 2, respectively.
5

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Molecular structures and crystal packing diagrams are shown in Figs. 1–7. The molecular
structures of two complexes are nearly like each other. They crystallize in the monoclinic crystal
system and P2 /n space group with Z= 4.
1
Table 1. Crystal data and structure refinement for C and C .
1
2
Compound
phthalimide
C32 H24 Cl2 N2 O2 P2 Pd
707.77
0.71073
173
hydrazine
C24 H22 Cl2 N2 P2 Pd, C H2 Cl2
662.60
1.54184
173
Empirical formula
Formula weight
Wavelength (Å)
T [K]
Crystal system
Monoclinic
Monoclinic
Space group
a [Å]
b [Å]
c [Å]
P2
1
/n (No. 14)
1
P2 /n (No. 14)
13.7612(3)
14.1511(3)
15.5930(3)
90
11.8569(3)
16.9266(4)
15.4657(4)
90
α [º]
β [º]
γ [º]
V [Å ]
Z
Density [g/cm ]
µ [mm ]
101.951(2)
90
2970.70(11)
4
1.582
0.946
105.573(2)
90
2989.97(13)
4
1.472
9.435
3
3
–1
F(000)
1424
1328
θ Min, Max [Deg]
Crystal Size [mm]
Index ranges
3.4, 29.4
0.10 x 0.30 x 0.30
–18 ≤ h ≤ 10,
4.0, 71.8
0.10 x 0.15 x 0.35
–14 ≤ h ≤ 14,
–20 ≤ k ≤ 20,
–18 ≤ l ≤ 18
5763
–
–
10 ≤ k ≤ 18,
18 ≤ l ≤ 19
Reflections collected
11068
R
int [%]
0.0236
6726/0/370
1.027
0.0991
5763/1/333
2.05
Data/restraints/parameters
Goodness-of-fit on F
2
R
1
[I>2 σ(I)]
0.0329
0.0663
5406
0.1308
0.4225
5171
wR [I>2 σ(I)]
Observed Data [I >2 σ(I)]
2
6

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o
Table 2. Selected bond lengths (Å) and bond angles ( ) for the solid-state structure of C
1
and C
2
.
Compound
Pd1–Cl1
Pd1–Cl2
Pd1–P1
Pd1–P2
P1–N1
P2–N1
N1–N2
P1–P2
C1
Compound
Pd1–Cl1
Pd1–Cl2
Pd1–P1
Pd1–P2
P1–N1
P2–N1
N1–N2
P1–P2
C2
2.3487(8)
2.3465(8)
2.2247(7)
2.1978(7)
1.734(2)
1.725(2)
1.394(3)
2.6658(9)
1.424(3)
1.410(3)
91.91(7)
74.14(3)
93.06(7)
125.76(16)
126.09(16)
100.83(11)
94.83(3)
94.15(3)
96.93(3)
168.92(3)
166.46(3)
121.26(19)
125.6(2)
2.4595(17)
2.4636(18)
2.211(2)
2.233(3)
1.695(9)
1.707(9)
1.404(13)
2.637(4)
0.88
0.88
93.1(3)
72.81(9)
92.0(3)
124.9(7)
133.0(7)
101.6(5)
91.87(8)
164.15(8)
98.13(6)
164.15(8)
169.78(8)
110.9
N2–C1
N2–H2A
N2–H2B
N2–C00A
N1–P1–Pd1
P1–Pd1–P2
N1–P2–Pd1
N2–N1–P1
N2–N1–P2
P1–N1–P2
P1–Pd1–Cl1
P2–Pd1–Cl2
Cl1–Pd1–Cl2
P2–Pd1–Cl1
P1–Pd1–Cl2
N1–N2–C1
N1–N2–C00A
Pd1–P1–N1
P1–Pd1–P2
Pd1–P2–N1
P1–N1–N2
P2–N1–N2
P1–N1–P2
Cl1–Pd1–P1
Cl2–Pd1–P2
Cl1–Pd1–Cl2
Cl1–Pd1–P2
Cl2–Pd1–P1
N1–N2–H2A
N1–N2–H2B
109.7
Crystallographic data and structural parameters (selected bond lengths and angles) of two
complexes are very close. They have square planar geometry with PNP chelate, and two chlorine
atoms are connected to the central metal. The bonding angles around the metal ion have a
remarkable deviation from square planer coordination, which is imposed by the strain in the
chelating ligands. These digressions are in the range of 1−18 degree from the standard square
°
°
planer. For example, P1–Pd1–P2 angles are acute (74.14(3) and 72.81(9) ), while Cl1−Pd1−Cl2
°
°
1 2
ones are obtuse (96.93(3) and 98.13(6) ) for C and C , respectively (Table 2). Metal-ligand
7

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[
38]
bond lengths are nearly the same as some of our previous compounds . The metal ion is at the
distance of 0.063(5) Å and 0.012 Å of the base plane defined by the atoms Cl1, Cl2, P1, P2,
sequentially in C and C .
1
2
C1
C2
Fig. 1. The ORTEP diagram of C and C . Ellipsoids are drawn at the 50% probability level.
1
2
In the structure of C , weak non-classic intermolecular hydrogen bonds of C4-H4···Cl1 and C5-
1
H5···Cl1, link the adjacent unit along the a‐ axis. Then, the non-classic C28-H28···Cl1, C16-
H16···Cl1, and C16–H16···Pd hydrogen bonds connect the chains in the ab-plane (Fig. 2). Inter-
layer interactions further interconnect adjacent 2D layers. These interactions are hydrogen bonds
(
C22-H22···O2, C23-H23···O2, and C19-H19···Cl2), C-H···π contacts (C23-H23···Cg(6), C5-
H5···Cg(6), C10-H10···Cg(3), C25-H25···Cg(7)), and Cl···π interaction [˂(Pd1−Cl2···Cg(4)) =
34.10(13)°, d(Cl2···Cg(4) = 3.763(7)Å]. Finally, the combination of all mentioned interactions
1
completes a three‐ dimensional network in the C crystal (Fig. 3). A summary of the parameters
1
for the interactions mentioned above is presented in Tables 3 and 4.
8

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Fig. 2. Assembly of molecules in the chain along the a-axis and adjoining of chains in the ab-plane through
hydrogen bonding interactions; Different chains are shown in different colors.
1
Fig. 3. (a) Side view of the crystal packing of C in the bc-plane; (b) the intermolecular interactions linking the
neighboring molecules in the bc-plane which shows how the 2D sheets are connected to the 3D construction;
9

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different colors show different molecular sheets. In (b) non-interacting hydrogen atoms have been omitted for visual
clearness.
Table 3. Hydrogen bonding interactions in C
1
2
and C (All distances in Å and angles in °).
Comp.
C1
...
D–H A
...
C4–H4 Cl1
D–H
0.95
0.95
0.95
...
...
∠ D–H A
127
Symm. Code
–1+x,y,z
H A
D A
2.82
2.90
3.13
3.480(3)
3.527(3)
3.844(3)
.
..
124
–1+x, y, z
C5–H5 Cl1
.
..
134
3/2–x,1/2+y,1/2–z
C16-H16 Cl1
C16-H16...Pd1
0.95
0.95
3.02
2.68
3.647(3)
3.607(3)
125
166
3/2–x,1/2+y,1/2–z
–1/2+x,3/2–y,–1/2+z
.
..
C19–H19 Cl2
.
..
0.95
0.95
0.95
2.59
2.51
2.80
3.192(3)
3.149(3)
3.565(3)
121
125
139
1–x,2–y,1–z
C22–H22 O1
.
..
1–x,2–y,1–z
3/2–x,–1/2+y,1/2–z
C23–H23 O2
.
..
C28–H28 Cl1
C
2
N2-H2B···Cl2
N2-H2B···Cl1A
C5-H5···N2
0.88
0.88
0.95
0.99
2.20
2.20
2.65
2.82
3.43(1)
3.61(1)
3.59(2)
3.733(18)
118
139
172
154
1/2+x,3/2–y,1/2+z
3/2–x,–1/2+y,1/2–z
1–x,1–y,1–z
C25-H25A···Cl2
1–x,2–y,–z
1 2
Table 4. C–H⋯π interaction geometries for C and C .
°
Comp.
CH⋯CgI
CH⋯Cg(Å)
3.810
3.342
3.746
3.729
C-H-Cg /
94
96
162
152
Symm. Code
1–x,2–y,1–z
–1/2+x,3/2–y,–1/2+z
1/2+x,3/2–y,–1/2+z
1–x,1–y,1–z
C
1
C23-H23···Cg(6)
C5-H5···Cg(6)
C10-H10···Cg(3)
C25-H25···Cg(7)
C2
C11-H11···Cg(4)
C4-H4···Cg(3)
C15-H15···Cg(5)
C24-H24···Cg(2)
C9-H9···Cg(4)
3.778
3.791
3.388
3.224
3.410
3.397
120
121
152
123
104
158
–1+x,y,z
1/2–x,–1/2+y,1/2–z
3/2–x,–1/2+y,1/2–z
1/2–x,1/2+y,1/2–z
–1/2+x,3/2–y,1/2+z
1/2+x,3/2–y,–1/2+z
C25-H25B···Cg(3)
1
Cg stands for the center of gravity of the mentioned ring: For C : Cg(3): C2-C7; Cg(6): C20-C25; Cg(7): C26-C31.
For C : Cg(2): C1-C6; Cg(3): C7-C12; Cg(4): C13-C18; Cg(5): C19-C24.
2
2
In the structure of C , intermolecular C-H···π interactions (C11-H11···Cg(4)), tie the adjacent
molecules along the a‐ axis (Fig. 4). Furthermore, different C-H···π interactions (C4-
H4···Cg(3), C15-H15···Cg(5), and C24-H24···Cg(2)) connect the chains in the ab-plane (Fig.
5
).
10

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2
Fig. 4. Formation of chains through C-H···π interactions in the crystal structure of C along the a-axis.
Fig. 5. Crystal packing of C
2
in the ab-plane by intermolecular C-H···π interactions; different colors present
different molecular chains.
Moreover, 2D sheets are associated together to arrange the whole 3D supramolecular
architecture (Fig. 6). The intermolecular interactions which link 2D sheets are a classic hydrogen
bonding between the hydrogen of the amine group and the Pd-attached chlorine atom (N2-
H2B···Cl2) along with the company of a non-classic hydrogen bond (C5-H5···N2) plus a C-
11

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,
H···π interaction (C9-H9···Cg(4)). As one can see in ORTEP diagram (Fig. 1) there is a
dichloromethane solvent in the asymmetric unit of this compound, which participates in the
crystal packing by interacting with four molecules of C . The C -solvent interactions are two
2
2
°
Cl···π interactions [˂(C25−Cl0A···Cg(5)) = 145 , d(Cl0A···Cg(5) = 3.817 Å] and
°
[
˂(C25−Cl1A···Cg(2)) = 172 , d(Cl4···Cg(2) = 3.488 Å], a C-H···π contact (C25-
H25B···Cg(3)), and two hydrogen bonds (N2-H2B···Cl1A, and Pd1-Cl2···H25A), Fig. 7. The
combination of these interactions makes a three‐ dimensional network in the solid state of C . A
2
summary of the parameters for the interactions mentioned above is presented in Tables 3 and 4.
Fig. 6. packing diagram of C (a) and (b) Joining of 2D sheets in ac and bc-plane, respectively; (c) Hydrogen bonds
2
;
and C-H···π interaction that connect molecules of two different sheets; different colors display different 2D-sheets.
In (c); non-interacting hydrogen atoms have been omitted for visual clarity.
12

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Fig. 7. Representation of solvent interactions in C ; non-interacting hydrogen atoms have been omitted for visual
2
clarity.
2
.4. The Heck coupling reactions
1 2
For catalytic activity evaluation of synthesized complexes, C and C in Heck coupling reaction,
optimization condition obtained in our previous work was used[38]. Optimized parameters such
as temperature (100°C), solvent (1:1 solution H O/DMF), base (K CO ), time (4h) and catalyst-
2
2
3
loading (0.005 mmol) were selected. These complexes were found to be efficient catalysts for the
Heck coupling reaction (Table 5).
The coupling of aryl iodides and bromides was great and afforded the desired products in good to
excellent conversions (entries 1–14). Using an electron donating group (EDG) as a substituent in
para position in aryl iodides led to no remarkable effect on conversions of desired products
(entries 4 and 5). Furthermore, due to the crowding effect, electron donating substituent on aryl
halides at the ortho position provided only low conversions than the para derivative (entries 6
and 7). Using aryl bromide as a substrate in Heck coupling reaction provided low conversions
than aryl iodides. Substituting electron withdrawing groups on aryl bromides increased the
catalytic activity and successfully coupled with olefins in good conversions (entries 8–14).
13

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a
Table 5. Heck reaction between aryl halides and olefins in presence of complexes C and C as a catalyst.
1
2
b
–1
c
Entry
Ar–X
Olefins
Conversion (%) (TOF (h )) (trans/cis product ratio)
C1
C2
Ph
1
2
I
100 (50)(94)
100 (50)(94)
O
I
I
100 (50)
100 (50)
(
CH ) CH
2 3 3
O
O
3
4
5
100 (50)
99 (49.5)
100 (50)
100 (50)
100 (50)
100 (50)
CH CH
2
3
O
Ph
Ph
MeO
MeO
I
I
O
O
(CH ) CH
2 3 3
O
I
6
7
94 (47)
86 (43)
95 (47.4)
90 (45)
OMe
I
(CH ) CH
3
2
3
O
O
OMe
Ph
Ph
Ph
8
9
CH CO
Br
Br
91 (45.5)
89 (44.4)
91 (45.5)
91 (45.5)
3
O
O
CH CO
3
(CH ) CH
2 3 3
1
1
1
0
1
2
CH CO
Br
90 (45)
86 (43)
49 (24.5)
93 (46.5)
89 (44.5)
53 (26.5)
3
CH CH
2 3
O
OHC
Br
O
O
Br
(
CH ) CH
2 3 3
O
1
3
4
Br
51 (25.5)
55 (27.5)
CH CH
2
3
O
1
Br
41 (20.5)(97)
45 (22.5)(97)
a
Reaction conditions: 1.0mmol of aryl halides, 1.2 mmol of olefins, 2mmol of K CO , 0.5mol% Complex, 3mL
2
2
3
b
c
H O/DMF, 4h. GC conversion. TOF = (mmol of product/mmol of catalyst)/hour.
Obtained results showed that C and C complexes are almost equally useful in the catalyzing of
1
2
Heck coupling reaction of olefins and aryl halides. Results indicated that replacement of different
substituents on P^P chelating ligands did not make any difference on the nature of the metal-
ligand interaction and both Pd–P bonds had same characters in related complexes which made
14

ACCEPTED MANUSCRIPT
them show equal activity in Heck coupling reaction. In comparison with previous reported
works, the catalytic reactivity of the presented complexes in this work was more favourable than
those which contain (O, N)[41] or (P, P)[19, 42] coordinated ligands, while in terms of reaction
conditions; harsh reaction situations, such as using high reaction temperatures and long reaction
times were not required hereon.
2
2
.5. Theoretical studies
.5.1. Thermodynamics. Two different structures are expected theoretically for L , which are
2
named as Pro.1 and Pro.2. Thermodynamic approaches have been used to calculate and compare
the Gibbs free energies and formation constants of the pathways which could lead to producing
these two structures from Pro.0. Indeed, the solvents play an important role in the binding
process and the preference of one structure than the other one and both the enthalpy and the
entropy of de-solvation are significant conditions in the overall computation of energy[43]. Thus,
to compare the binding selectivity of PPh
site or the secondary one, we have to compare the free Gibbs energies and formation constants
K) of corresponding structures that can be calculated from the known equation ∆G = −RT LnK.
2
Cl to Pro.0, which can connect to a primary nitrogen
(
According to the thermodynamic cycle shown in Scheme 3, the change in Gibbs free energy of
ꢂ
the reaction between Pro.0 and PPh Cl in solution, ∆G , is equal to the sum of gas-phase Gibbs
2
ꢀꢁ
free energy of reaction, ∆Gꢂ , and change in solvation energies, ∆G ꢄꢂ ꢅꢆꢇꢈ, as following equations
ꢃꢀꢄ
present it:
Pro.0 (aq) + PPh Cl (aq) → [Pro.1 / Pro.2] (aq) + HCl (aq)
(1)
(2)
2
ꢂ
= ∆Gꢂ + ∆Gꢂ
ꢄꢅꢆꢇ
∆
G
ꢀꢁ
ꢃꢀꢄ
15

ACCEPTED MANUSCRIPT
ꢂ
= G (HCl + [Pro.1 / Pro.2]) − Gꢂ (PPh Cl) − G (Pro.0)
ꢂ
ꢂ
∆
∆
G
G
(3)
(4)
ꢃꢀꢄ
ꢃꢀꢄ
ꢃꢀꢄ
2
ꢃꢀꢄ
ꢂ
ꢄꢅꢆꢇ
= G (HCl + [Pro.1 / Pro.2]) − Gꢂ (PPh Cl) − G (Pro.0)
ꢂ
ꢂ
ꢄꢅꢆꢇ
ꢄꢅꢆꢇ
2
ꢄꢅꢆꢇ
Scheme 3. Illustration of proposed thermodynamic cycle for reaction.
Calculated Gibbs free energies and formation constants for Pro.1 and Pro.2 structures in
dichloromethane solution are given in Table 6 (detailed information exist in Table S2 of
supplementary data). Acquired data by different methods, basis sets, and solvation models have
proven that Pro.1 always has larger formation constants rather than Pro.2. For example, related
values of LogK at M06-2X/6-31G** are 6.00, 5.53 and 5.57 for Pro.1 and 3.56, 3.65 and 3.68 for
Pro.2 in SMD, CPCM, and PCM models. These results are in agreement with experimental
affairs which express that the preferred product is Pro.1. The overall reaction ∆G ꢀꢂ amounts are
ꢁ
−
1
−1
exergonic by 8.19, 7.55 and 7.60 kcal.mol for Pro.1 and 4.86, 4.98 and 5.02 kcal.mol for
Pro.2 in the mentioned level of theory and solvation models, which indicate that this reaction is a
spontaneous process at 0 °C (reaction temperature).
16

ACCEPTED MANUSCRIPT
0
a
Table 6. Calculated ꢀG and LogK values for the formation of Pro. 1 and Pro. 2 in CH Cl .
2
2
ꢍ
ꢍ
∆
ꢉ
ꢉ
ꢎꢏꢐꢑ. ꢒꢓ
ꢎꢏꢐꢑ. ꢒꢓ
∆ꢉ ꢎꢏꢐꢑ. ꢔꢓ
ꢊꢋꢌ
ꢊꢋꢌ
logK
ꢎꢏꢐꢑ. ꢒꢓ ꢎꢏꢐꢑ. ꢔꢓ
logK
ꢍ
ꢍ
Method
∆ꢉꢋꢕꢎꢏꢐꢑ. ꢒꢓ ∆ꢉꢋꢕꢎꢏꢐꢑ. ꢔꢓ
ꢍ
ꢍ
∆
∆ꢉ ꢎꢏꢐꢑ. ꢔꢓ
ꢌꢑꢖꢗ
ꢌꢑꢖꢗ
B3LYP/6-
−7.28
−4.14
3
11++G**
SMD
0.04
0.59
0.53
0.66
0.53
0.50
−7.24
−6.69
−6.75
−3.48
−3.61
−3.64
5.31
4.90
4.95
2.55
2.64
2.67
CPCM
PCM
M06/6-31G**
SMD
−7.40
0.01
0.60
0.59
−4.83
0.69
0.64
0.57
−7.39
−6.80
−6.81
−4.14
−4.19
−4.26
5.42
4.98
4.99
3.03
3.65
3.66
CPCM
PCM
M06-2X/6-
−8.19
−5.62
3
1G**
SMD
0.00
0.64
0.59
0.76
0.64
0.60
−8.19
−7.55
−7.60
−4.86
−4.98
−5.02
6.00
5.53
5.57
3.56
3.65
3.68
CPCM
PCM
a
ꢂ
values are given as bold text and the values of ∆Gꢂ obtained from different models are in italic.
∆G
ꢃꢀꢄ
ꢄꢅꢆꢇ
2
.5.2. Kinetics. According to thermodynamic calculations, Pro.1 has a greater formation
constant than Pro.2. However, yet it is not clear that Pro.1 is the only product of the reaction. To
address the reason of this manner, we have had to investigate which pathway of possible
products is more favorable in terms of energy. In our computational modeling, mono-substituted
hydrazine (Pro.0) is chosen as the substrate in energy profile. As depicted in Scheme 4, starting
from Pro.0, two different pathways are conceivable for binding the second phosphine (pathways
I and II). In pathway, I, the cleavage of the N2–H2 and P–Cl bonds and formation of P–N2 and
H–Cl bonds occurs through a one-step quadrilateral shape transition structure (TS1), which leads
to the formation of Pro.1. In comparison, in pathway II, the N1–H1 and P–Cl bonds are cleaved,
and P–N1 and H–Cl are formed by passing transition structure (TS2) and finally Pro.2 is formed.
17

ACCEPTED MANUSCRIPT
−1
Scheme 4. Energy profile calculated for the formation of Pro.1 and Pro.2 in kcal.mol which obtained from the
M06-2X/aug-cc-pVTZ calculations.
18

ACCEPTED MANUSCRIPT
‡
−1
Table 7. Activation (∆ꢘ ) and reaction (∆ꢘ ) energies (kcal.mol ) calculated for the formation of Pro.1 and
ꢙꢚꢛ
Pro.2.
∆ꢜ‡
TS1)
∆ꢜ‡
(TS2)
Method
∆ꢜꢝꢞꢟ
ꢎꢏꢐꢑ. ꢒꢓ
∆ꢜꢝꢞꢟ
ꢎꢏꢐꢑ. ꢔꢓ
(
CPCM
M06/6-31G**
12.07
17.20
15.56
16.35
14.73
20.32
26.12
24.19
24.90
23.52
−4.56
−3.93
−6.71
−4.95
−7.44
−0.60
−0.20
−2.02
−1.36
−2.63
M06/Def2-TZVP
M06/aug-cc-pVTZ
M06-2X/Def2-TZVP
M06-2X/aug-cc-pVTZ
SMD
M06/6-31G**
13.69
18.61
16.11
17.81
15.26
21.07
24.80
23.54
22.58
22.03
−4.60
−4.01
−6.82
−4.96
−7.51
−2.41
−1.86
−2.46
−1.53
−2.79
M06/Def2-TZVP
M06/aug-cc-pVTZ
M06-2X/Def2-TZVP
M06-2X/aug-cc-pVTZ
2
.5.3. NBO analysis. Investigation of metal-ligand interaction by NBO analysis in Table 8
reveals that the electronic delocalization from the lone pair of the nitrogen donors in both
(2)
complexes has the same character. In the C1 complex, total E values of Lp(N8) → σ*(P4–C22
and P4–C33) is 12.35 and Lp(N8) → σ*(P5–C44 and P5–C55) is 12.29. These same values of
(
2)
(2)
E indicate that all P–Ph bonds have the same character. In the C2 complex, total E values of
Lp(N6) → σ*(P4–C10 and P4–C21) and Lp(N6) → σ*(P5–C32 and P5–C43) are 16.50 and
1
6.22, which are relatively equal and illustrate the same trend observed in
1
C . We also became
interested in checking out the other nitrogen lone pair transfer in studied complexes. In
1
C ,
(
2)
relatively equal values of E from Lp(N9) to
bonds have the same character and the total value of E is 14.42 kcal.mol . In the C2 complex,
the N7 lone pair could flow to *(P4–N6) and *(P5–N6), which the total value is 13.98. Close
values of Lp(N) → σ*(P–N) in these two complexes reveal that P–N bonds in C1 and C2 are
σ*(P4–N8 and P5–N8) demonstrate that both P–N
(2)
–1
σ
σ
19

ACCEPTED MANUSCRIPT
naturally close to each other. Furthermore, Wiberg bond indices (WBIs) values of metal-ligand
interaction in Table S4 confirm that not only the two Pd–P bond interactions are similar in each
of the complexes, but also the same in both of them (all Pd–P WBIs in C1 and C2 are 0.66).
(2)
Table 8. Values of E at M06–2X/Def2–TZVP level of theory.
ꢋ
ꢠꢎꢔꢓ
7.64
12.72
7.26
5.09
5.00
7.29
Complex
Donor
Acceptor
C
1
LP (1) N8
LP (1) N8
LP (1) N8
LP (1) N8
LP (1) N8
LP (1) N8
BD*(1) N 9 – C 10
BD*(1) N 9 – C 11
BD*(1) P 4 – C 22
BD*(1) P 4 – C 33
BD*(1) P 5 – C 44
BD*(1) P 5 – C 55
LP (1) N9
LP (1) N9
LP (1) N9
LP (1) N9
BD*(1) P 4 – N 8
BD*(1) P 5 – N 8
BD*(2) O 6 – C 10
BD*(2) O 7 – C 11
6.92
7.50
58.83
50.02
C2
LP (1) N 6
LP (1) N 6
LP (1) N 6
LP (1) N 6
LP (1) N 6
LP (1) N 6
BD*(1) N 7 – H 8
BD*(1) N 7 – H 9
BD*(1) P 4 – C 10
BD*(1) P 4 – C 21
BD*(1) P 5 – C 32
BD*(1) P 5 – C 43
5.52
5.69
7.87
8.63
8.33
7.89
LP (1) N 7
LP (1) N 7
BD*(1) P 4 – N 6
BD*(1) P 5 – N 6
12.76
1.22
a
–1
The values are reported in kcal.mol .
3
. Experimental
3
.1. Materials and method
All the starting materials are commercially available and have been used without any further
purification. All reactions and manipulations have been performed under an argon atmosphere
using standard Schlenk techniques unless otherwise stated. Ph PCl, N-Aminophthalimide, and
2
Hydrazine dihydrochloride have been purchased from Sigma-Aldrich. The starting material
20

ACCEPTED MANUSCRIPT
[
44]
[
MCl
2
(COD)] (M = Pd, COD = 1,5-cyclooctadiene)
has been prepared according to the
literature procedures. Solvents have been dried using the appropriate reagents.
3
.1.1. General procedure for the synthesis of the ligands. 1g (4.55mmol)
chlorodiphenylphosphine (Ph PCl) was slowly added to a solution of N-Aminophthalimide (0.39
2
g, 2.25 mmol) and triethylamine (0.46 g, 4.55mmol) or Hydrazine dihydrochloride (0.24 g, 2.25
mmol) and triethylamine (0.92 g, 9.10 mmol) in dichloromethane (20 mL) at 0 ̊C . The resulting
suspension was stirred for 2h and then the solvent was removed by filtration through a sintered
Schlenk tube. The remaining solid was washed with distilled water and ethanol consecutively;
then dried in vacuum to produce a white solid. Physical and spectroscopic data of them are
presented, as following:
N,N-bis(diphenylphosphino)- N-Aminophthalimide (L1). [(Ph P) NNC O C H ]. Yield: 0.96 g,
2 2 2 2 6 4
◦
31
1
8
7
1
0%. mp 203–206 C. P–{1H} NMR δ (ppm): 77.5 (s). H NMR δ (ppm): 7.72 (m, 8H, Ph),
–
1
.52 (m, 12H, Ph), 7.86 (m, 2H, Ph), 7.66 (m, 2H, Ph). IR data (KBr, cm ): 1787, 1731s,
433m, 1207, 1100m, 990m; 878s, 741, 702s, 524m, 450s.
N,N-bis(diphenylphosphino) Hydrazine (L ). [(Ph P) NNH ]. Yield: 0.67 g, 75%. mp 140–
2
2
2
2
◦
31
1
1
45 C. P–
{
1H}
NMR
). IR data (KBr, cm ): 3444w, 3050m, 2930m, 1475m, 1429s, 1095s, 938s,
46s, 744s, 694s, 616m, 497m, 446m.
δ (ppm): 80.03 (s), H NMR δ (ppm): 7.42 (m, 8H, Ph), 7.33 (m, 12H,
–
1
Ph), 5.30 (s, 2H, NH
2
8
3
.1.2. General procedure for the synthesis of complexes. A solution of [PdCl (COD)] (0.171
2
g, 0.600 mmol) and the corresponding ligand (0.318 g or 0.240 g for 1 and 2, respectively; 0.600
mmol) in CH Cl (10 ml) was stirred at RT for 1h. The volume of the solvent was concentrated
2
2
to 1–2 ml under reduced pressure and addition of Et O (15 ml) gave the palladium complexes as
2
21

ACCEPTED MANUSCRIPT
yellow solids which were isolated by filtration. Their physical and spectroscopic data are
presented, as follows:
3
1
1
[
PdCl {(Ph P) NNC O C H }] (C ). Yield: 0.382 g, 90%. P–{1H} NMR δ (ppm): 67.06 (s). H
2 2 2 2 2 6 4 1
–
1
NMR
δ (ppm): 7.63 (m, 8H, Ph), 7.51 (m, 12H, Ph), 8.08 (m, 4H, Ph). IR data (KBr, cm ):
1
794, 1740s, 1435m, 1345m, 1205, 1104m, 1034, 990m; 884s, 742, 704s, 572m, 508s.
3
1
1
[PdCl
2 2 2 2 2
{((Ph P) NNH }] (C ). Yield: 0.318 g, 92%. P–{1H} NMR δ (ppm): 70.0 (s). H NMR δ
–
1
(
ppm): 7.89 (m, 8H, Ph), 7.55 (m, 12H, Ph), 2.91 (s, 2H, NH ). IR data (KBr, cm ): 3443w,
2
3
052m, 2925m, 1477m, 1434s, 1105s, 929s, 875s, 749s, 690s, 616m, 648s, 565m, 502s.
3
.2. Crystal structure determination
Single crystal X-Ray diffraction data have been collected for both of compounds on an Agilent
Gemini Ultra diffractometer equipped with an Eos CCD area detector and using either Mo-K
radiation ( =0.71073 Å) or Cu-K radiation ( =1.5418 Å). The data have been collected at
73K using an Oxford Cryosystems Cryostream 600. The data have been processed with
α
λ
α
λ
1
[
45]
CrysAlisPro . Semi-empirical absorption corrections have been carried out using the Multi-
[
46]
[47]
Scan program. The structures have been solved by direct methods using SHELXT and have
[
48]
[48]
been refined with full matrix least-squares refinement by SHELXL-2013 within Olex2 . All
non-hydrogen atoms have been refined anisotropically. Hydrogen atoms have been added at
calculated positions and refined using a riding model based on the parent atom. The CIF files
have been deposited with the CCDC and have been given the deposition numbers 1570872 and
1
845356 for C1 and C2, respectively.
3
.3. General Procedures for the Heck Reaction
22

ACCEPTED MANUSCRIPT
A flask was charged with complex (0.5 mol%) along with an appropriate amount of aryl halide
(
1.0 mmol), olefin (1.2 mmol), K CO (2.0 mmol), and H O/DMF (3 mL) and a magnetic stir
2 3 2
bar. The mixture was heated to 100 °C with stirring for a specified period of time. After the
reaction mixture was cooled to room temperature, hydrochloric acid (1 M, 6 mL) was added and
the product was extracted with diethyl ether (3
from the organic layer. The diethyl ether solution was washed with water (3
MgSO , and evaporated to dryness under reduced pressure to afford the desired product, which
×15 mL). The aqueous solution was separated
×15 mL), dried over
4
was then washed with hexane (3×5 mL). The purity of the compounds was checked by GC and
yields are based on the aryl halide. Assignments of products were made by comparison with
authentic samples.
4
. Computational details
To perform thermodynamic calculations, the geometries of all species in the gas-phase were fully
[
49, 50]
optimized with the standard 6-311++G** basis set at B3LYP
and also 6-31G** basis sets at
[
51]
[52]
[53]
M06 and M06-2X levels of theory using the Gaussian 09 set of programs. Vibrational
frequency analysis calculated at the same levels of theory indicated that optimized structures
were at the stationary points, corresponding to local minima without any imaginary frequency.
[
54]
To calculate solvation energies, the Solvation Model based on Density (SMD)
,
[
55-57]
The Polarizable Continuum Model (PCM)
and the Conductor-like Polarizable Continuum
Model (CPCM) was used at all above-mentioned levels of theory in CH Cl solvent and the
[
58]
2
2
temperature of 273 K. To carry out kinetic calculations, Gaussian 09 was also used to fully
optimize all the structures at the M06 level of DFT with the standard 6-31G** basis set in
CH Cl and the temperature of 273 K using the SMD and CPCM solvation models. Frequency
2
2
23

ACCEPTED MANUSCRIPT
calculations were accomplished at the same level of theory as those for the structural
optimization. Transition structures were located using the Berny algorithm. Intrinsic Reaction
Coordinate (IRC) calculations were used to confirm the connectivity between transition
[
59, 60]
structures and minima
. To further refinement of the energies obtained from M06/6-31G**
calculations, single-point energy calculations carried out for all of the structures with larger basis
sets (Def2-TZVP and aug-cc-pVTZ) using the CPCM and SMD solvation models at M06 and
M06-2X levels of theory. The electronic properties, nature of the coordination interactions and
the Wiberg bond indices (WBIs) of the
1 2
C and C complexes were investigated through DFT
[
61]
calculations by NBO analyses at the M06-2X/Def2-TZVP level on the optimized structure at
the same level.
5
. Conclusions
We have synthesized and characterized two N, N-bis(diphenylphosphino)-amine ligands and
their Pd(II) complexes ( and ). X-ray crystallography reveals square planar structures for the
complexes with one chelating P–N–P ligand and two coordinated chlorines. Investigations of the
C
1
C
2
...
...
systematics of crystal packing indicate that CH Cl and NH Cl interactions are the main factors,
controlling the supramolecular assembly of the complexes. To synthesize N,N-
bis(diphenylphosphino) Hydrazine from ((diphenylphosphanyl) hydrazine), two probable
pathways are considerable which give Pro.1 and Pro.2. Thermodynamic and kinetic studies of
the formation constants and the possible mechanism of the reactions determine that Pro.1 (N,N-
bis(diphenylphosphino) Hydrazine) should be the only product. C1 and C2 represent high
catalytic activity in the Heck coupling reactions of aryl bromides and iodides with various
olefins. Herein, results demonstrate that replacing different substituents in P^P chelated ligand
24

ACCEPTED MANUSCRIPT
do not affect the catalytic activity which is also surveyed by NBO, in which the WBI data show
that P−Pd interactions are the same in both complexes.
Conflicts of interest
There are no conflicts by the authors to declare”.
Acknowledgments
Financial support of this work by Tarbiat Modares University is gratefully acknowledged.
Notes and references
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