Concerted pathway to the mechanism of the Anilinolysis of Bis(N,N-diethylamino)phosphinic chloride in Acetonitrile

Article abstract of DOI:10.1071/CH16202

The kinetics of the nucleophilic substitution reactions of bis(N,N-diethylamino)phosphinic chloride with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated in MeCN at 65.0°C. The deuterium kinetic isotope effects (DKIEs) are secondary inverse (kH/kD<1: 0.706-0.947) and the magnitudes of the secondary inverse DKIEs (kH/kD) increase constantly as the nucleophiles are changed from weakly basic to strongly basic anilines. The magnitudes of the selectivity parameters are ρX(H)≤-6.34, and βX(H)≤2.24 with substituted anilines and ρX(D)≤-6.13 and βX(D)≤2.17 with deuterated anilines. A concerted SN2 mechanism involving predominant backside attack is proposed based on the kH/kD values with substituent X.

Full text of DOI:10.1071/CH16202

CSIRO PUBLISHING
Aust. J. Chem. 2017, 70, 101–105
Full Paper
http://dx.doi.org/10.1071/CH16202
Concerted Pathway to the Mechanism of the Anilinolysis of
Bis(N,N-diethylamino)phosphinic Chloride in Acetonitrile
Hasi Rani Barai
Department of Mechanical Engineering, Yeungnam University, Gyeongsan 712-749,
Korea. Email: hrbarai@ynu.ac.kr
The kinetics of the nucleophilic substitution reactions of bis(N,N-diethylamino)phosphinic chloride with substituted
anilines (XC H NH ) and deuterated anilines (XC H ND ) are investigated in MeCN at 65.08C. The deuterium kinetic
isotope effects (DKIEs) are secondary inverse (k /k , 1: 0.706–0.947) and the magnitudes of the secondary inverse
6
4
2
6
4
2
H
D
DKIEs (k /k ) increase constantly as the nucleophiles are changed from weakly basic to strongly basic anilines. The
H
D
magnitudes of the selectivity parameters are rX(H) ¼ ꢀ6.34, and b
¼ 2.24 with substituted anilines and r
¼ ꢀ6.13
X(H)
X(D)
and bX(D) ¼ 2.17 with deuterated anilines. A concerted S 2 mechanism involving predominant backside attack is
N
proposed based on the k /k values with substituent X.
H
D
Manuscript received: 29 March 2016.
Manuscript accepted: 10 June 2016.
Published online: 4 July 2016.
Introduction
Results and Discussion
Phosphoryl and thiophosphoryl transfer reactions have been
studied extensively because of their importance in biochemistry
and organometallic chemistry as well as their usefulness in
synthesis. The phosphoryl transfer reactions of bis(N,N-
diethylamino)phosphinic chloride (4) with substituted anilines
The observed pseudo-first-order rate constants for the reactions
were denoted as kobsd and calculated using Eqn 1 for all reactions
under pseudo- first-order conditions with a large excess of
aniline as a nucleophile. The k values were negligible (k E 0)
in acetonitrile. The second-order rate constants (kH(D)) were
determined from at least five concentrations of anilines. The
linear plots of Eqn 1 suggest that there is no base catalysis or
noticeable side reactions and that the whole reaction can be
described by Scheme 1.
0
0
(XC H NH ) and deuterated anilines (XC H ND ) were
6 4 2 6 4 2
investigated kinetically in acetonitrile (MeCN) at 65.0 ꢁ 0.18C
(
Scheme 1). The kinetics are discussed based on the selectivity
parameters and deuterium kinetic isotope effects (DKIEs).
This study examines the substituent effects, DKIEs, and
mechanism of the phosphoryl transfer reactions. In addition, the
kinetic results of the present work are compared with the kinetic
results of the anilinolyses of dimethylphosphinic chloride
kobsd ¼ k0 þ kHðDÞ½XC6H4NH2ðD2Þꢂ
ð1Þ
[
1]
The second-order rate constants, kH with X-anilines, kD
values with deuterated X-anilines, the DKIEs (k /k ), and
(
1: Me P(¼O)Cl), diethylphosphinic chloride (2: Et P(¼O)
2
2
[2]
H
D
Cl), and their counterparts with the substituents containing
two nitrogen atoms adjacent to the positive charge centre P, e.g.,
bis(N,N-dimethylamino)phosphinic chloride (3: (Me N) P
selectivity parameters for Hammett rX(H and D) and Brønsted
bX(H and D) values, are summarised in Table 1. The pK (X)
values of the X-anilines in water were used to obtain the
Brønsted bX values in MeCN, and this procedure could be
a
2
2
[3]
(
¼O)Cl).
[4–19]
[20–23]
justified experimentally
and theoretically.
The
values of pK (X) and sX of the deuterated X-anilines were
a
O
P
assumed to be identical to those of the X-anilines. Perrin et al.
reported that the basicity of the b-deuterated analogues of
benzylamine, N,N-dimethylaniline, and methylamine increase
ϩ 2NL C H X
2
6
4
Cl
(
CH CH ) N
3 2 2
by ,0.02 pK units per deuterium, and that these effects are
(
CH CH ) N
a
24–26]
3
2 2
[
additive.
Therefore, the pK (X) values of deuterated
a
O
X-anilines may be slightly greater than those of X-anilines,
but the difference is too small to be taken into consideration.
ϩ
Ϫ
MeCN
5.0ЊC
P
ϩ XC H NL ϩ Cl
6 4 3
6
NLC H X
Fig. 1 (log kH(D) versus s ) shows the Hammett plots and
X
(
CH CH ) N
6
4
3
2 2
Fig. 2 (log kH(D) versus pK (X)) shows the Brønsted plots with
X. All the free energy correlations with X were linear without a
(
CH CH ) N
a
3
2 2
[
30,31]
[32–35]
breaking point
more electron-donating substituent X and the rate decreased
or region.
The rate increased with a
Scheme 1. Reactions of bis(N,N-diethylamino)phosphinic chloride (4)
with XC NH (D) in MeCN at 65.08C.
6
H
4
2
2
Journal compilation � CSIRO 2017
www.publish.csiro.au/journals/ajc

1
02
H. R. Barai
5
21 21
Table 1. Second-order rate constants (kH(D) 3 10 , M
s
), selectiv-
) of the reactions of bis
NH (D ) in
with a more electron-withdrawing substituent X in the nucleo-
philes, which is the nature of a typical nucleophilic substitution
reaction with positive charge development at the nucleophilic
A
), and DKIEs (k
ity parameters (q
X
and b
X
H
/k
D
(
N,N-diethylamino)phosphinic chloride (4) with XC
MeCN at 65.08C
6
H
4
2
2
N atom (r , 0) in the transition state (TS). The rates with
X
deuterated anilines were faster than those with anilines. The
magnitudes of the selectivity parameters of rX(H) ¼ ꢀ6.34
and bX(H) ¼ 2.24 with anilines were greater than those
5
5
X
k
H
ꢃ 10
k
D
ꢃ 10
H D
k /k
B
B
G
4
4
3
-MeO
339 ꢁ 1
358 ꢁ 1
0.947 ꢁ 0.004
0.900 ꢁ 0.002
0.850 ꢁ 0.008
0.805 ꢁ 0.020
0.786 ꢁ 0.006
0.714 ꢁ 0.004
0.706 ꢁ 0.003
(
rX(D) ¼ ꢀ6.13 and b
¼ 2.17) with deuterated aniline, sug-
-Me
-Me
78.0 ꢁ 0.1
14.7 ꢁ 0.1
86.7 ꢁ 0.1
17.3 ꢁ 0.1
X(D)
gesting that they are more sensitive to the substituent effects of
the anilines compared with those of the deuterated anilines, and
there is a corresponding change in the reaction mechanism from
strongly to weakly basic anilines. The investigated DKIEs were
secondary inverse (k /k ,1) and the magnitudes of the DKIEs
H
5.16 ꢁ 0.01
6.41 ꢁ 0.01
3
4
3
-MeO
1.14 ꢁ 0.01
1.45 ꢁ 0.01
-Cl
-Cl
0.215 ꢁ 0.002
0.0281 ꢁ 0.0003
0.342 ꢁ 0.001
0.0398 ꢁ 0.0001
H
D
C
E
ꢀ
r
X(H,D)
6.34 ꢁ 0.09
6.13 ꢁ 0.08
decreased constantly as the nucleophile was changed from the
more electron-donating to more electron-withdrawing substitu-
ent X variations: e.g. X ¼ 4-MeO (k /k ¼ 0.947) to X ¼ 3-Cl
D
F
b
X(H,D)
2.24 ꢁ 0.06
2.17 ꢁ 0.05
A
The s values were taken from ref. [27]. The pK
in water were taken from ref. [28].
B
Standard deviation.
a
values of X-anilines
H D
(
k /k ¼ 0.706).
H D
The second-order rate constants (k ) with unsubstituted
H
C
Correlation coefficient, r ¼ 0.999.
aniline, natural bond order (NBO) charges at the reaction centre
P atom (B3LYP/6–311þG(d,p) level of theory) in the gas
D
r ¼ 0.996.
E
[
36]
r ¼ 0.999.
phase,
the reactions of 1–4 with XC H NH (D ) in MeCN are sum-
Brønsted coefficients (b
), and DKIEs (k /k ) of
X(H) H D
F
r ¼ 0.997.
G
2
2
2 1/2
6
4
2
2
Standard error (¼ 1/k
D
[(Dk
H
) þ (k
H
/k
D
) ꢃ (Dk
D
) ] ) from ref. [29].
marised in Table 2. Counting the magnitudes of the positive
charges at the reaction centre P atom, the anilinolysis rate
should be 4 . 3 . 2 . 1 but the observed rate sequence was
Ϫ2
Ϫ3
Ϫ4
1
... 2 .. 3 . 4, which is completely the opposite to expec-
tations for the electronic influence of the two ligands. Therefore,
the positive charge at the reaction centre P atom does not play a
major role in determining the reactivity and mechanism of the
phosphinic chloride systems. The second-order rate constants
for the anilinolyses of the above-mentioned phosphinic chlor-
rX(H) ϭ Ϫ6.34
rX(D) ϭ Ϫ6.13
ꢀ4
ꢀ4
ꢀ4
ides were k ¼ 78200 ꢃ 10 , 1890 ꢃ 10 , 0.318 ꢃ 10 , and
H
ꢀ4
Ϫ5
Ϫ6
Ϫ7
ꢀ1 ꢀ1
0
.297 ꢃ 10
M s for 1–4, respectively, giving a relative
rate ratio of 263 299 (1) : 6364 (2) : 1.1 (3) : 1.0 (4) in MeCN at
55.08C. From the observed rate ratio, it is conclusive that the
anilinolysis rate sequence of 1 ... 2 .. 3 . 4 is inversely
proportional to the sizes of the two ligands of the phosphinic
[
1–3,16]
Ϫ0.30
Ϫ0.15
0
0.15
0.30
0.45
chloride system:
Me N) 3 , (Et N, Et N) 4.
(Me, Me) 1 , (Et, Et) 2 , (Me N,
2
sX
2
2
2
The DKIEs (k /k ) are strong tools for clarifying the
H
D
X
Fig. 1. Hammett plots (log kH(D) versus s ) with X of the reactions of
reaction mechanism. When the k /kD values are greater than
H
6 4 2 2
bis(N,N-diethylamino)phosphinic chloride (4) with XC H NH (D ) in
unity, primary normal (k /k . 1.0), the partial deprotonation of
H
D
MeCN at 65.08C.
aniline occurs in a rate-limiting step by hydrogen bonding (e.g. a
[
7,16,18]
frontside attack transition state (TSf) shown in Fig. 3).
On the other hand, the DKIEs are only secondary inverse
k /k , 1.0) when an increase in steric congestion occurs in
Ϫ2
(
H
D
the bond-making process (e.g. backside attack transition state
(TSb) shown in Fig. 3), because the N–H(D) vibrational fre-
Ϫ3
[
1–3]
bX(D) ϭ 2.17
quencies increase upon going to the TS.
Therefore, DKIEs
provided a useful means of determining the TS structures in the
nucleophilic substitution reactions, and particularly through
changes in substituents, any alterations in the TS structures.
The incorporation of deuterium in the nucleophile has an
advantage in that the a-DKIEs resemble only the degree of
bond formation, especially for the secondary inverse DKIEs.
Therefore, the greater the extent of bond formation, the greater
the steric congestion, and the k /k values become smaller.
Ϫ4
bX(H) ϭ 2.24
Ϫ5
Ϫ6
Ϫ7
H
D
3.5
4.0
4.5
5.0
5.5
NBO charges at the reaction centre P atom, Brønsted coeffi-
cients (bX(H)/bX(D)), DKIEs (k /k ), and anilinolysis mechan-
isms for reactions of 1–7 with XC H NH (D ) in MeCN are
pK (X)
H D
a
6
4
2
2
summarised in Table 3. Comparing the magnitudes of the NBO
charges at the reaction centre P atom in the phosphinic chlorides,
the observed sequences are 4 . 3 . 6 . 7 . 5 . 2 . 1, and for
a
Fig. 2. Br o¨ nsted plots (log kH(D) versus pK (X)) with X of the reactions
6 4 2 2
of bis(N,N-diethylamino)phosphinic chloride (4) with XC H NH (D ) in
MeCN at 65.08C.

Anilinolysis of Bis(N,N-diethylamino)phosphinic Chloride
103
3 21 21
3 10 , M s
Table 2. Summary of the second-order rate constants (k
H
) with C
6
H
5
NH
2
, NBO charges at the reaction centre P atom, Brønsted
coefficients (bX(H)), and DKIEs (k
H
/k
D
6 4 2 2
) for the reactions of 1–4 with XC H NH (D ) in MeCN
3
A
B
Substrate
k
H
ꢃ 10
Charge at P
b
X(H)
k
H
/k
D
Ref.
C
D
F
1
2
3
4
: Me
: Et P(=O)Cl
: (Me N) P(=O)Cl
: (Et N) P(=O)Cl
2
P(=O)Cl
7820
1.793
1.817
2.165
2.194
1.62
0.56
2.27
2.24
0.703–0.899
0.828–0.974
0.686–0.955
0.706–0.947
[1]
E
2
189
[2]
G
G
H
H
2
2
0.0318
0.0297
[3]
2
2
This work
A
B
The values with unsubstituted aniline at 55.08C.
Strongly/weakly basic anilines.
ꢀ3
C
ꢀ1 ꢀ1
M s
The value of k
H
¼ 7.820 ꢃ 10
at 55.08C was obtained by extrapolation in the Arrhenius plot (r ¼ 0.999) with kinetic data: k
H
¼ 776, 1010, and
ꢀ3
ꢀ1 ꢀ1
1
610 ꢃ 10
M
s
at 0.0, 5.0, and 15.08C, respectively, from ref. [1].
D
Values at 15.08C.
¼ 189 ꢃ 10
E
ꢀ3
ꢀ1 ꢀ1
s
The value of k
H
M
at 55.08C was obtained by extrapolation in the Arrhenius plot (r ¼ 0.999) with kinetic data: k
ꢀ1 ꢀ1
M s at 40.0, 50.0, and 60.08C, respectively, from ref. [2].
H
¼ 117, 162, and
ꢀ
3
2
11 ꢃ 10
F
Values at 50.08C.
Experimental kinetic value. See ref. [3] and Table S2 (Supplementary Material).
G
H
Values at 65.08C.
‡
‡
backside nucleophilic attack involving an in-line-type TSb
(Fig. 3). The magnitudes of the k /kD values constantly
XH C
4
6
H
C H X
6 4
O
P
H
O
P
decreased with a more electron-withdrawing substituent X
(4-MeO - 3-Cl) in the nucleophiles. This means that the steric
congestion in the TS invariably increases as the anilines become
weakly basic. In other words, the frown reactivity of the
nucleophile results in a greater degree of bond formation.
Therefore, the value of k /k (0.706–0.947) indicates very stern
N
N
Cl
H
Et N
H H
NEt2
2
Cl
NEt2
Et N
2
TSf
TSb
H
D
steric congestion in the TS, suggesting a greater extent of bond
formation.
Fig. 3. Frontside attack involving a hydrogen bonded, four-centre-type
TSf and backside attack involving in-line-type TSb.
The activation parameters, enthalpies, and entropies of the
reaction were determined (Table S2, Supplementary Material).
The enthalpies of activation were small and the entropies of
activation were large negative values. The small value of
enthalpy and large negative value of entropy are typical for
the aminolyses of P¼O (and P¼S) systems. Therefore, the
reaction mechanism by means of the activation parameters is not
easy for the aminolyses of P¼O (and P¼S) systems.
the b values found the sequence is 3 . 4 . 7 . 1 . 6 . 2. It is
clear that the b values do not depend on the positive charge
development at the reaction centre P atom. The variation in
magnitude in b values indicates that they do not have any major
role on the charge development either at the positive reaction
centre P atom or at the nucleophilic N atom in the reaction
system. The concerted mechanism with predominantly backside
nucleophilic attack was for the anilinolysis of 1 (k /k ¼ 0.703–
[38]
H
D
Conclusion
[
1]
0
.899) and the concerted mechanism with predominantly
The nucleophilic substitution reactions of bis(N,N-diethyla-
mino)phosphinic chloride (4) with substituted anilines
frontside attack via a hydrogen-bonded four-centre-type TS
1]
[
was for the anilinolysis of 5 (k /k ¼ 1.62–2.10). The degree
H
D
(XC H NH ) and deuterated anilines (XC H ND ) were
6 4 2 6 4 2
of steric hindrance was the major factor that determined both the
reactivity of the phosphinates and the direction of the nucleo-
philic attack on the phosphinates. Other factors, such as the
vibrational frequencies and bending and stretching modes,
investigated kinetically in MeCN at 65.08C. The magnitudes of
secondary inverse deuterium kinetic isotope effects (k /k )
H
D
constantly increased as the nucleophiles were changed from
weakly basic to strongly basic anilines. A concerted mechanism
with a predominant backside attack TSb is proposed based on
the k /k values (secondary inverse) with substituent X.
[
1]
governed the mechanism of the reactions for 5. A concerted
mechanism with a predominant TSb was based on the secondary
[
2]
inverse DKIEs for the anilinolyses of 2 (k /k ¼ 0.828–0.974)
H D
H
D
[
3]
and 3 (k /k ¼ 0.686–0.955). A concerted S 2 mechanism
H
D
N
was based on both secondary inverse and primary normal DKIEs
Experimental
[
37]
for 6 (k /k ¼ 0.673–1.10). The obtained DKIEs implied that
H
D
Materials and Synthetic Procedure of Deuterated Anilines
the fraction of a frontside attack increased as the aniline was
more basic. A hydrogen-bonded, four-centre-type TS was sug-
gested for a frontside attack, while the trigonal bipyramidal
pentacoordinate TS was suggested for a backside attack. A
concerted mechanism with a partial frontside nucleophilic
attack through a hydrogen-bonded, four-centre type TS was
HPLC grade acetonitrile (water content ,0.005 %) and anilines
were purchased from Sigma Aldrich and used without further
purification. Deuterium oxide (99.99 atom % D) was purchased
from Sigma Aldrich and used as it was received. Deuterated
[
1–3]
anilines were synthesised as previously reported.
Deuter-
[
7]
for the anilinolysis of 7. Nevertheless, there is no correlation
between the k /k and bX values. In the present work, the
ated anilines were synthesised by refluxing anilines in
deuterium oxide (99.99 atom % D) with a few drops of HCl as
catalyst at 858C for 72 h, and collected after numerous
H
D
DKIEs are secondary inverse with all the anilines shown in
Table 1. The secondary inverse DKIEs are strengthened by a
1
attempts. H NMR analysis confirmed .98 % deuteration.

1
04
H. R. Barai
H D
Table 3. Summary of NBO charges at the reaction centre P atom, Brønsted coefficients (bX(H)/bX(D)), DKIEs (k /k ), and anilinolysis mechanisms
6 4 2 2
for the reactions of 1–7 with XC H NH (D ) in MeCN
A
Substrate
Charge at P
b
X(H)/bX(D)
k
H
/k
D
Mechanism
Ref.
B
B
C
D
D
1
2
3
4
5
6
7
: Me
: Et P(=O)Cl
: (Me N) P(=O)Cl
: (Et N) P(=O)Cl
: MePhP(=O)Cl
: cHex P(=O)Cl
: Ph P(=O)Cl
2
P(=O)Cl
1.793
1.817
2.165
2.194
1.821
1.863
1.844
1.62/1.56
0.56/0.52
2.27/2.22
2.24/2.17
0.88/0.80
0.67/0.56
1.69/1.62
0.703–0.899
0.828–0.974
0.686–0.955
0.706–0.947
concerted
concerted
concerted
concerted
concerted
concerted
concerted
[1]
C
D
D
E
E
F
2
[2]
2
2
[3]
2
2
This work
[1]
E
1.62–2.10
E
2
0.673–1.10
F
1.42–1.82
[37]
[7]
2
A
Strongly/weakly basic anilines. Stepwise: ‘Bond formation/breaking’ indicates a stepwise mechanism with a rate-limiting bond formation and with a rate-
limiting leaving group expulsion from the intermediate, respectively.
B
Values at 15.08C.
C
Values at 50.08C.
D
Values at 65.08C.
Values at 60.08C.
Values at 55.08C.
E
F
Bis(N,N-diethylamino)phosphinic chloride (4), commercially
available, was used without further purification.
(Ϫ0.353)
∠ 105.88
∠
108.96
Cl
(
Ϫ1.098)
∠
102.69
H
Methods of Kinetics Measurement
O
H
C
∠ 116.59
(
ϩ2.194)
Rates and selectivity parameters were calculated as previously
described.
∠ 112.25
P
[1–3]
C
Rates were measured conductimetrically using
(Ϫ0.907)
H
H
H
N
the conductivity bridge which was a self-made computer auto-
mated A/D converter conductivity bridge. Pseudo-first-order
rate constants (kobsd) were calculated by curve fitting analysis of
the decay profiles in Origin 8.5. The concentrations used in this
H
N
(
Ϫ0.883)
C
C
H
H
C
C
H
H
H
C
H
H
ꢀ3
∠
109.52
work were [substrate] ¼ 5 ꢃ 10 M and [X-anilines] ¼ 0.10,
H
0
.15, 0.20, 0.25, 0.30 M. The k values were at least the
obsd
C
H
average of three runs, which were reproducible within ꢁ3 %.
H
H
Second-order rate constants, k , were calculated from the
H(D)
slope of a plot of kobsd versus [X-anilines]. The selectivity
parameters, rX(H/D), were obtained from the slope of the plot of
Fig. 4. The B3LYP/6–311þG(d,p) geometry of bis(N,N-diethylamino)
phosphinic chloride (4) in the gas phase.
log kH(D) versus s and b
from the slope of the plot of log
X
X(H/D)
kH(D) versus pK (X).
a
ligands. The molecular orbital theoretical structure shows that
the two nitrogens, oxygen, and chlorine have distorted tetrahe-
dral geometry with the phosphorus atom at the reaction centre.
Synthetic Procedure of Product Analysis
Bis(N,N-diethylamino)phosphinic chloride (4) was reacted with
excess aniline for more than 15 half-lives at 65.08C in MeCN.
Solvent was evaporated under reduced pressure. The product
mixture was treated with diethyl ether by a work-up process with
Supplementary Material
The analytical and spectroscopic data obtained from charac-
1
13
terisation of the products, such as H NMR (Fig. S1), C NMR
dilute HCl and dried over anhydrous MgSO . The product was
4
3
Fig. S2), P NMR (Fig. S3), mass spectrometry spectra
1
(
then isolated through column chromatography (30 % ethyl
acetate/n-hexane). The results are as follows (see Supplemen-
tary Material):
(
Fig. S4), the B3LYP/6–311þG(d,p) geometry of bis(N,N-
diethylamino)phosphinic chloride (4) in the gas phase (Fig. S5
and Table S1) and Table S2 are available on the Journal’s
website.
C H N P(¼O)NHC H : Colourless liquid. d (300 MHz,
8
20
2
6
5
H
CDCl & TMS) 1.08–1.12 (m, 12H), 3.13–3.32 (m, 8H), 5.42
3
(
1
d, J 6, 1H), 6.99–7.28 (m, 5H). d (150 MHz, CDCl & TMS)
C 3
Acknowledgements
3.1, 40.2, 118.7, 122.8, 129.3, 138.9. d (243 MHz, CDCl &
P 3
þ
This work was supported by an Internal Research Grant of Yeungnam
University. The author thanks the Department of Chemistry, especially the
biophysical laboratory, Yeungnam University for support in doing some
work there. They also thank Emeritus Prof. Hai Whang Lee, Department of
Chemistry, Inha University, Korea, for fruitful discussion to prepare the
manuscript.
TMS) 14.4 (1P, s, P¼O). m/z (LC-MS, EI) 283 [M ].
Theoretical Studies of Bis(N,N-diethylamino)phosphinic
Chloride (4)
The B3LYP/6–311þG(d,p) geometry, bond angles, and NBO
[36]
charges of 4 in the gas phase
are calculated by using the
B3LYP/6–311þG(d,p) level in Gaussian 09 and is shown on
the optimised structure of 4 in Fig. 4, a series of optimised
structures and details are given in the Supplementary Material
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