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Spectrochimica Acta Part A 67 (2007) 837–846

Prediction of 31P nuclear magnetic resonance


chemical shifts for phosphines
Jianbo Tong a , Shuling Liu b , Shengwan Zhang a,∗ , Shengshi Z. Li c,d,∗∗
aCollege of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, PR China
bCollege of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, PR China
c College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, PR China
d State Key Laboratory of Chemo/Biosensing and Chemometrics, Changsha 410082, PR China

Received 2 June 2006; received in revised form 28 August 2006; accepted 30 August 2006

Abstract
Quantitative relationships of the 31 P NMR chemical shifts of the phosphorus atoms in 291 phosphines with the atomic ionicity index (INI)
and stereoscopic effect parameters (ε␣ , ε␤ , ε␥ ) were primarily investigated in this paper for modeling some fundamental quantitative structure-
spectroscopy relationships (QSSR). The results indicated that the 31 P NMR chemical shifts of phosphines can be described as the quantitative
equation by multiple linear regression (MLR): δp (ppm) = −174.0197 − 2.6724 INI + 40.4755ε␣ + 15.1141ε␤ − 3.1858ε␥ , correlation coefficient
R = 0.9479, root mean square error (rms) = 13.9, and cross-validated predictive correlation coefficient was found by using the leave-one-out
procedure to be Q2 = 0.8919. Furthermore, through way of random sampling, the estimative stability and the predictive power of the proposed
MLR model were examined by constructing data set randomly into both the internal training set and external test set of 261 and 30 compounds,
respectively, and then the chemical shifts were estimated and predicted with the training correlation coefficient R = 0.9467 and rms = 13.4 and
the external predicting correlation coefficient Qext = 0.9598 and rms = 10.8. A partial least square model was developed that produced R = 0.9466,
Q = 0.9407 and Qext = 0.9599, respectively. Those good results provided a new, simple, accurate and efficient methodology for calculating 31 P NMR
chemical shifts of phosphines.
© 2007 Published by Elsevier B.V.

Keywords: Quantitative structure-spectroscopy relationships (QSSR); 31 P NMR chemical shifts of phosphorus; Phosphines; Atomic ionicity index (INI); Stereoscopic
effect parameters

1. Introduction paid attention by many chemists and scientists. So far, large


of studies for 31 P NMR chemical shifts simulation and predic-
Nuclear magnetic resonance (NMR) spectroscopy is one of tion have been done by many scientists. Kuivalainen et al. [17]
the most valuable tool for studying constitution, state and struc- reported 31 P NMR chemical shifts of o,o-dialkyl o-aryl phos-
ture of compounds [1–5], especially 31 P NMR technique plays phorothionates correlated with the bond critical points (BCP)
an important role in finding or building the structure–property lying between phosphorus and its neighboring atoms. Robert et
relationships of many phosphorus compounds in the field of al. [18] developed a theoretical methodology for the analysis of
chemistry, biology and medicine [6–15], and so on. However, the 31 P NMR spectroscopy in vanadium phosphorus oxide (VPO)

weakness of using 31 P for NMR spectroscopy is the lower sen- systems. Chruszcz et al. [19,20] calculated NMR spectroscopy
sitivity, longer spin-relaxation times, and difficult measurement of hydroxypyridin-3-yl-methyl phosphonic acid and pyridine-
for minimal quantity compound of phosphorus [16]. Therefore, 2-phosphono-4-carboxylic acid as well as structural parameters
the prediction of 31 P NMR spectroscopy is more and more of the compounds. West [21] developed a new approach, based
on neural networks for predicting 31 P NMR chemical shift val-
ues, and further studied the factors influencing the accuracy of
∗ Corresponding author. Tel.: +86 351 7011787; fax: +86 351 7011688.
∗∗
predicting the 31 P NMR chemical shifts of the compounds [22].
Corresponding author at: College of Chemistry and Chemical Engineering,
Chongqing University, Chongqing 400044, PR China. Tel.: +86 23 6510667.
Based on density functional theory (DFT) and gauge-including
E-mail addresses: zswan@sxu.edu.cn, aswan@sxu.edu.cn (S. Zhang), atomic orbital (GIAO), Ruiz-Morales and Ziegler [23] carried
zlli-cqu@163.com (S.Z. Li). out theoretical study on 31 P NMR chemical shifts in phosphine-

1386-1425/$ – see front matter © 2007 Published by Elsevier B.V.


doi:10.1016/j.saa.2006.08.041
838 J. Tong et al. / Spectrochimica Acta Part A 67 (2007) 837–846

substituted metal carbonyls of the type Mo(CO)5 PR3 . Bosque electronegativity of the atom changes no longer. Based on above
and Sales [24] selected seven descriptors from a pool com- standpoint, Nie et al. [25] defined the atomic ionicity index (INI):
posed of 708 structural descriptors of phosphine compounds  XG
XE − XA
and calculated the 31 P NMR chemical shifts by using multiple INI = × 100, XE = (2)
linear regression and computational neural networks, respec- XA N
tively, however, this is tedious and time-consuming. In this where XE in Eq. (2) denoting the equilibrium electronegativ-
paper, based on the above-mentioned literature research work, ity of the atom A, XG denoting sum of electronegativity of
according to the principle of nuclear magnetic resonance spec- atoms and groups which directly bonded with atom A, the N
troscopy, and using the connection among 31 P NMR chemical means amount of atoms and groups (included atom A) which
shifts of 291 phosphines, the atomic ionicity index (INI) [25] co-jointed with atom A. Obviously, the INI of the phosphorus
and stereoscopic effect parameter εi (i = α, β, γ) four descrip- atom in PH3 is minimal, and the INI value is lowest among the
tors which could indicate influencing the 31 P NMR chemical phosphines. Actually, INI indicates magnitude of electronega-
shifts of phosphorus atoms. The aforementioned descriptors tivity change after the atoms form molecule, that is, the bigger
are utilized to develop models for predicting 31 P NMR chem- electronegativity changes, the higher the INI value will be.
ical shifts, and using multiple linear analysis and partial least
square regression, best quantitative structure-spectroscopy rela- 2.2. Relationship of atomic ionicity index and stereoscopic
tionships models were obtained. The models were simple and effect parameters with 31 P NMR spectroscopy
convenient for calculating 31 P NMR chemical shifts in phos-
phines, which have provided a higher degree of accuracy than According to the principle of the nuclear magnetic resonance
previous multiple linear regression methodology in the litera- spectroscopy, the maximum absorption peak in nuclear magnetic
ture [24] (R = 0.9284, rms = 16.1 ppm). Moreover, each item of resonance spectroscopy can be expressed as
the models had the explicit physical significance. For phosphine
molecules which have certain structure, we only need to cal- υsample − υreference γB γB0 (1 − σ)
δ= × 106 , υ= =
culate the INI and the εi (i = α, β, γ) of phosphorus atom in υreference 2πs 2πs
phosphines, the 31 P NMR chemical shifts of phosphorus atom (3)
in the phosphines can be computed. The developed models not
only clarified the quantitative relationship between 31 P NMR In Eq. (3), σ is the shield constant and B0 is the intensity of addi-
chemical shifts of phosphines and characterization parameters tional magnetic field. It is well known that 31 P NMR chemical
of their molecular structures, but also provided a new method shifts of the nuclei are related to deshielding effect. Deshield-
for calculating 31 P NMR chemical shifts of phosphines. And it ing effect has direct relevance to XE , that is, deshielding effect
also gave theoretical laws for forecasting 31 P NMR chemical has direct relevance to INI. In view of the above discussion, INI
shifts and studying on the mathematical relationship between is considered as one of numerical representative of molecular
structures and property of phosphines. structure. So the 31 P NMR chemical shifts of the phosphorus
nuclei are related to INI of phosphorus atoms. As phosphine
molecules have special tetrahedron structure, the presence of
2. Theoretical section
attached and nearby atoms have a profound effect on 31 P NMR
chemical shift of the central phosphorus atom. The effect of sub-
2.1. Atomic equilibrium electronegativity and atomic
stituents on NMR chemical shifts can be ignored from as far as
ionicity index
four bonds away or directly through space [28]. Here the effect
of substituents with six bonds away phosphorus atom was once
Two or more atoms with different electronegativity bonded,
calculated on 31 P NMR chemical shifts. The results showed that
the electronegativity of each atom incline to equalization [26].
atoms or groups, which apart from four bonds away phosphorus
Zhou [27] pointed out “electronegativity equalization of atom
nuclear, have a slight effect on the 31 P NMR chemical shifts.
does not mean every atom has equal electronegativity; even if
Based on the aforementioned results and discussion we used
the same kind atoms are placed in the dissymmetry position, it
stereoscopic effect parameters for predicting 31 P NMR chemi-
gives or gets different electronegativity”. Based on aforemen-
cal shifts. We defined the stereoscopic effect parameters εi (i = ␣,
tioned standpoint, Nie et al. [25] had put forward a new formula
␤, ␥):
to calculate electronegativity of groups, based on the Pauling’s
atomic electronegativity. The formula is defined by the following εi = ni qi/C (4)
expression:
     among Eq. (4), the variable ni means the number of non-
1  1  1 
n1l n2l nkl
hydrogen atoms which is i-substituents, qi/C means the
XG = ... Xkl . . . (1)
n1l n2l nkl Pauling’s electronegativity of non-hydrogen atoms divided
l=1 l=1 l=1
by that of carbon atom, such as the molecule PH(CF3 )2 ,
The electronegativity of atom A in molecule is different from ε␣ = 2qC/C = 2 × 1 = 2, ε␤ = 6qF/C = 6(3.98/2.55) = 9.3647,
the element of A as freedom due to forming molecules. Once ε␥ = 0.
molecules come into being, atom A and surroundings atoms or The aforementioned results prompted us that INI and stereo-
groups’ electronegativity attains balance state, the equilibrium scopic effect parameters can be considered as molecular property
J. Tong et al. / Spectrochimica Acta Part A 67 (2007) 837–846 839

and that they can be used as molecular descriptors for modeling ment between experimental and estimated data indicated that the
31 P NMR chemical shifts, so 31 P NMR chemical shifts of phos- proposed descriptors INI, ε␣ , ε␤ and ε␥ in our calculations are
phines can be modeled according to the following regression correct.
equation:
3.2. Validation of the MLR model
δp = a + b(INI) + cε␣ + dε␤ + eε␥ (5)
Model validation is crucial to QSAR/QSPR/QSSR model-
3. Results and discussion
ing. The predictive capability of a QSSR model should be tested
through model validation. Cross-validation is one of the most
3.1. Multilinear regression model
often used model validation methods. However, the recent study
of Tropsha et al. [31–33] showed that there are no evident rela-
The data set was comprised of 291 phosphines, their 31 P
tionships between the value of Q2 and actual predictive power
NMR chemical shifts, INI, ε␣ , ε␤ and ε␥ parameters were given
of a QSSR model, and external validation is required. The pre-
in Table 1 . Application of regression analysis showed that 31 P
dictive power of a model on external dataset can be expressed
NMR chemical shifts of phosphines can be judged by the fol-
by Q2ext in contrast to the original Q2 [32]:
lowing multiple linear regression expression:
 
test
i=1 (yi − ŷi )
2
δp = −174.0197 − 2.6724 INI + 40.4755ε␣ + 15.1141ε␤ Qext = 1 − test
2
(7)
i=1 (yi − ȳtr )
2
− 3.1858ε␥ , n = 291, m = 4, R = 0.9479,
rms = 13.9, F = 632.4384 (6) where yi are the observed value of test dataset, ŷi the calculated
value of test dataset, and ȳtr is the mean value of observed value
In Eq. (6), n is the number of samples used for model build- of training set.
ing, m the number of descriptors involved in the developed In this paper, in order to prove the modeling stability and
model, R the multiple correlation coefficient, rms is the root the predictive power of our proposed MLR model the way of
mean square error, and F is the Fisher’s statistics. To elimi- random sampling is being used to construct the training set and
nate the effect of over-fitting on the prediction of a model and external prediction set is the first step. Two hundred and ninety-
get good estimation and prediction capabilities, the variables are one compound data set of Table 1 was split randomly into a 261
further screened by stepwise multiple regression (SMR) method member training set and an external prediction set of 30 com-
(Table 2). pounds, and then the chemical shifts of the external prediction set
Table 2 indicates that the value of correlation coefficient (R) samples were estimated. The calculated results were also listed
increases gradually with increasing of the number of variables in CSMR column of Table 1. The training set had R = 0.9467 and
(m). When four variables are involved in the multiple linear rms = 13.4. The external predicting Qext = 0.9598 and rms = 10.8
regression (MLR) models, the R reaches to the highest. In the for the prediction set of 30 phosphines. In addition, the model
same way, the variation of Q for leave-one-out procedure cross- was tested through the cross-validation using the leave-one-out
validation (LOO) increases with the increase of the value of method. In this way, each time one molecule was removed from
m, which shows over-fitting phenomenon is not involved. The the set, and a model was developed with the remaining n − 1
change of root mean square error (rms) with increase of the molecules. At each step, the 31 P NMR chemical shift was pre-
number of variables showed a reverse process. The values of dicted with the obtained model for the removed molecule. The
rms in MLR models and rmsCV for leave-one-out procedure results for the leave-one-out methods were also listed in CSCV
cross-validation (LOO) decrease with the increase of the num- column of Table 1. Another cross-validated parameter of interest
ber of variables rapidly. The value of R represents the estimate is the predictive correlation coefficient, which is usually named
capability of model, and the result of cross-validation character- as cross-validation Q2 . The highest value of Q2 indicates the best
izes the prediction ability and stability of the developed model. predictive power. Once again Q2 (0.8919) was in favor of model-
Considering the values of R and Q, the optimal number of vari- 6. A comparison of calculated or predicted 31 P NMR chemical
ables to construct our model was 4. The 1-, 2-, 3-, 4-variable shifts values and experimental data for 291 phosphines is
models were showed as above. The statistics of t was 21.884 Fig. 1.
for ε␣ and the multicollinearity statistics variable inflation fac- One can observe that calculated or predicted 31 P NMR chem-
tor (VIF) was 1 for 1-variable model; t were 16.725 and 13.286 ical shifts values agree well with experimental data, however,
for ε␣ and ε␤ , VIF were 1.375 and 1.375 for 2-variable model; t the prediction results show that there are some samples that
were 22.504, 21.761 and −13.944 for ε␣ , ε␤ and INI, VIF were have large deviations. It needs to be emphasized that 31 P NMR
1.381, 1.786 and 1.469 for 3-variable model; t were −13.638, chemical shifts experimental values were not obtained under the
27.160, 26.996 and −10.281 for INI, ε␣ , ε␤ and ε␥ , and VIF same experimental conditions of solvent and temperature in all
were 1.543, 1.394, 1.865 and 1.308 for 4-variable model. Since cases. Since the 31 P NMR chemical shifts depend on the exper-
no over-fitting existed, it was no need to eliminate variables. imental conditions – concentration, temperature, and solvent –
The estimated values of 31 P NMR chemical shifts of 291 phos- the wide diversity in the origin of the measures may result in an
phines were obtained using above 4-variable model listed in increase of the error between experimental and calculated values
CSMO column of Table 1. From Table 1 can know: a good agree- [24].
840 J. Tong et al. / Spectrochimica Acta Part A 67 (2007) 837–846

Table 1
Calculated and experimental values of 31 P NMR chemical shifts and calculated parameters for phosphines

No. Compound INI ε␣ ε␤ ε␥ CSEX a CSMO b CSMR c CSCV d CSCal e

1 PH2 (p-OMeC6 H4 )f 3.2865 1.0000 2.0000 2.0000 −125.8 −118.5 −118.3 −118.3 −118.7
2 PH2 Me 1.3413 1.0000 0 0 −163.5 −137.1 −137.1 −136.3 −137.2
3 PH2 CF3 16.5811 1.0000 4.6824 0 −129.0 −107.1 −106.7 −105.6 −108.3
4 PH2 Et 1.5913 1.0000 1.0000 0 −128.0 −122.7 −122.6 −122.5 −122.9
5 PH2 (n-octyl) 1.6747 1.0000 1.0000 1.0000 −128.5 −126.1 −126.0 −126.0 −126.2
6 PH2 (s-Bu) 1.9030 1.0000 2.0000 1.0000 −120.5 −111.6 −111.5 −111.3 −111.8
7 PH2 Cy 2.0068 1.0000 2.0000 2.0000 −110.0 −115.1 −114.9 −115.2 −115.2
8 PH2 Bz 2.0071 1.0000 1.0000 2.0000 −120.9 −130.2 −130.1 −130.4 −130.2
9 PH2 (n-Bu) 1.6689 1.0000 1.0000 1.0000 −140.0 −126.1 −126.0 −125.7 −126.2
10 PH2 (i-Bu) 1.7158 1.0000 1.0000 2.0000 −151.0 −129.4 −129.3 −128.8 −129.4
11 PH2 (n-pentyl)f 1.6735 1.0000 1.0000 1.0000 −139.0 −126.1 −126.0 −125.7 −126.2
12 PH2 (C6 F5 ) 9.7797 1.0000 2.0000 5.1216 −183.0 −145.8 −145.6 −144.4 −145.9
13 PH2 (o-BrC6 H4 ) 3.9703 1.0000 2.0000 3.1608 −130.6 −124.0 −123.9 −123.8 −124.1
14 PH2 (p-BrC6 H4 ) 3.3276 1.0000 2.0000 2.0000 −124.0 −118.6 −118.5 −118.4 −118.8
15 PH2 (o-ClC6 H4 ) 4.2237 1.0000 2.0000 3.2392 −127.5 −124.9 −124.8 −124.9 −125.0
16 PH2 (CH2 CH2 CN) 2.0156 1.0000 1.0000 1.0961 −135.0 −127.3 −127.2 −127.1 −127.5
17 PH2 (p-ClC6 H4 ) 3.4121 1.0000 2.0000 2.0000 −124.1 −118.8 −118.7 −118.7 −119.0
18 PH2 (p-FC6 H4 ) 3.7591 1.0000 2.0000 2.0000 −125.4 −119.7 −119.6 −119.6 −123.4
19 PH2 (o-OHC6 H4 ) 3.7922 1.0000 2.0000 3.1059 −147.4 −123.3 −123.2 −122.7 −118.0
20 PH2 (p-tol) 3.0434 1.0000 2.0000 2.0000 −124.5 −117.8 −117.7 −117.6 −118.3
21 PH2 (p-EtC6 H4 )f 3.2911 1.0000 2.0000 2.0000 −125.5 −118.5 −118.4 −118.3 −118.7
22 PH2 (p-NMe2 C6 H4 ) 3.1495 1.0000 2.0000 2.0000 −126.1 −118.1 −118.0 −117.9 −111.0
23 PH2 (CH2 CH2 NH2 ) 1.7908 1.0000 1.0000 1.1922 −150.4 −127.0 −126.9 −126.4 −127.1
24 PH2 Ph 3.0057 1.0000 2.0000 2.0000 −118.7 −117.7 −117.6 −117.7 −117.9
25 PH2 (i-Pr) 1.8413 1.0000 2.0000 0 −106.0 −108.2 −108.1 −108.3 −108.6
26 PH2 (t-Bu) 2.0902 1.0000 3.0000 0 −82.0 −93.8 −93.6 −94.2 −94.2
27 PH2 (CH CH2 ) 2.1187 1.0000 1.0000 0 −135.7 −124.1 −124.0 −123.8 −124.4
28 PH2 (o-tol) 3.1176 1.0000 2.0000 3.0000 −130.9 −121.2 −121.1 −120.9 −121.3
29 PH2 (o-SHC6 H4 ) 3.2466 1.0000 2.0000 2.9373 −131.7 −121.3 −121.2 −121.1 −121.4
30 PHMe2 2.3402 2.0000 0 0 −99.5 −99.3 −99.2 −99.3 −99.1
31 PH(CF3 )2 f 32.8196 2.0000 9.3647 0 −50.7 −39.2 −38.5 −37.1 −41.2
32 PHEt2 2.8402 2.0000 2.0000 0 −55.5 −70.4 −70.2 −70.6 −70.4
33 PH(n-Bu)2 2.9954 2.0000 2.0000 2.0000 −69.5 −77.2 −77.0 −77.3 −77.0
34 PH(CH2 CH2 CN)2 3.6895 2.0000 2.0000 2.1922 −75.0 −79.7 −79.5 −79.7 −79.5
35 PHPh2 5.6689 2.0000 4.0000 4.0000 −41.0 −60.5 −60.2 −60.7 −60.3
36 PHMeEt 2.5902 2.0000 1.0000 0 −77.0 −84.9 −84.7 −85.0 −84.8
37 PHMe(n-Pr) 2.6530 2.0000 1.0000 1.0000 −87.0 −88.2 −88.1 −88.2 −88.0
38 PHMe(n-Bu) 2.6678 2.0000 1.0000 1.0000 −86.0 −88.3 −88.1 −88.3 −88.1
39 PHMePh 4.0046 2.0000 2.0000 2.0000 −72.3 −79.9 −79.7 −80.0 79.7
40 PH(i-Bu)2 3.0890 2.0000 2.0000 4.0000 −82.5 −83.8 −83.7 −83.9 −83.4
41 PH(i-Pr)2 f 3.3402 2.0000 4.0000 0 −26.4 −41.5 −41.2 −41.8 −41.7
42 PHEtPh 4.2546 2.0000 3.0000 2.0000 −43.7 −65.5 −65.2 −65.6 −65.4
43 PH(n-Pr)2 2.9658 2.0000 2.0000 2.0000 −73.0 −77.1 −77.0 −77.2 −76.9
44 PH(n-pentyl)2 3.0034 2.0000 2.0000 2.0000 −69.4 −77.2 −77.1 −77.3 −77.0
45 PHPh(CH2 CH2 NH2 ) 4.4543 2.0000 3.0000 3.1922 −52.0 −69.8 −69.6 −69.9 −69.6
46 PH(n-Pr)Ph 4.3174 2.0000 3.0000 3.0000 −53.4 −68.8 −68.6 −68.9 −68.6
47 PH(i-Bu)Ph 4.3790 2.0000 3.0000 4.0000 −60.2 −72.2 −72.0 −72.3 −71.9
48 PH(n-Bu)Ph 4.3322 2.0000 3.0000 3.0000 −52.4 −68.9 −68.6 −69.0 −68.7
49 PH(i-Pr)Ph 4.5046 2.0000 4.0000 2.0000 −26.4 −51.0 −50.7 −51.3 −51.0
50 PH(s-Bu)Ph 4.5662 2.0000 4.0000 3.0000 −30.1 −54.4 −54.1 −54.6 −54.3
51 PH(cyclopentyl)Phf 4.6701 2.0000 4.0000 4.0000 −37.1 −57.8 −57.6 −58.0 −57.6
52 PH(t-Bu)Ph 4.7534 2.0000 5.0000 2.0000 −5.7 −36.6 −36.3 −37.0 −36.7
53 PH(C6 F5 )2 19.2169 2.0000 4.0000 10.2431 −143.0 −116.6 −116.3 −115.2 −116.4
54 PHPh(C6 F5 ) 12.4429 2.0000 4.0000 7.1216 −92.2 −88.6 −88.3 −88.5 −88.4
55 PH(m-ClC6 H4 )2 6.3333 2.0000 4.0000 4.0000 −41.5 −62.3 −62.0 −62.4 −62.1
56 PH(m-FC6 H4 )2 7.1758 2.0000 4.0000 4.0000 −40.9 −64.5 −64.3 −64.7 −64.4
57 PH(p-FC6 H4 )2 7.1758 2.0000 4.0000 4.0000 −44.0 −64.5 −64.3 −64.7 −64.4
58 PH(m-ClC6 H4 )(p-CF3 C6 H4 ) 6.6027 2.0000 4.0000 4.0000 −42.0 −63.0 −62.7 −63.2 −62.9
59 PH(p-CF3 C6 H4 )2 6.8721 2.0000 4.0000 4.0000 −42.7 −63.7 −63.5 −63.9 −63.6
60 PH(p-MeOC6 H4 )(o-tol) 6.0616 2.0000 4.0000 5.0000 −44.4 −64.7 −64.5 −64.9 −64.5
61 PH(p-MeOC6 H4 )2 f 6.2306 2.0000 4.0000 4.0000 −45.4 −62.0 −61.7 −62.1 −61.9
62 PH(o-tol)2 5.8927 2.0000 4.0000 6.0000 −59.1 −67.5 −67.2 −67.6 −67.1
63 PH(m-tol)2 5.7443 2.0000 4.0000 4.0000 −40.2 −60.7 −60.4 −60.9 −60.5
64 PH(p-tol)2 5.7443 2.0000 4.0000 4.0000 −42.9 −60.7 −60.4 −60.9 −60.5
J. Tong et al. / Spectrochimica Acta Part A 67 (2007) 837–846 841

Table 1 (Continued )

No. Compound INI ε␣ ε␤ ε␥ CSEX a CSMO b CSMR c CSCV d CSCal e

65 PH(p-t-BuC6 H4 )2 5.7991 2.0000 4.0000 4.0000 −43.9 −60.9 −60.6 −61.0 −60.7
66 PHBu(CH2 CH2 NH2 ) 3.1176 2.0000 2.0000 2.1922 −37.4 −78.2 −78.0 −78.5 −77.9
67 PHCy(CH2 CH2 CN) 3.6804 2.0000 3.0000 3.0961 −37.4 −67.4 −67.2 −67.7 −67.2
68 PMe3 3.3390 3.0000 0 0 −62.0 −61.5 −61.4 −61.5 −61.0
69 P(CF3 )3 49.0582 3.0000 14.0470 0 −2.5 28.6 29.8 44.4 26.0
70 P(CH2 OH)3 8.6473 3.0000 3.3176 0 −24.8 −25.6 −25.2 −25.6 −25.5
71 P(CH2 NEt2 )3 f 6.3596 3.0000 3.5765 6.0000 −65.3 −34.6 −34.4 −34.4 −33.9
72 P(CN)3 20.7192 3.2882 0 0 −135.7 −96.3 −96.0 −91.1 −96.5
73 PMe2 (CF3 ) 18.5788 3.0000 4.6824 0 −26.9 −31.5 −31.0 −31.7 −32.0
74 PMe2 (CH2 Cl) 6.0788 3.0000 1.2392 0 −42.0 −50.1 −49.9 −50.3 −49.8
75 PMe2 Et 3.5890 3.0000 1.0000 0 −48.5 −47.1 −46.9 −47.0 −46.6
76 PMe2 (t-Bu) 4.0879 3.0000 3.0000 0 −28.7 −18.2 −17.9 −18.0 −17.9
77 PMe2 CH(NMe2 )2 5.2700 3.0000 2.3843 4.0000 −46.2 −43.4 −43.2 −43.3 −42.7
78 PMe2 Cy 4.0046 3.0000 2.0000 2.0000 −43.1 −39.4 −39.2 −39.4 −38.9
79 PMe2 (p-MeC6 H10 ) 4.0148 3.0000 2.0000 2.0000 −42.5 −39.5 −39.2 −39.4 −38.9
80 PMe2 Ph 5.0034 3.0000 2.0000 2.0000 −46.9 −42.1 −41.9 −42.0 −41.6
81 PMe2 (o-ClC6 H4 )f 6.2215 3.0000 2.0000 3.2392 −49.4 −49.3 −49.1 −49.3 −48.7
82 PMe2 (o-BrCH2 C6 H4 ) 5.5362 3.0000 2.0000 3.0000 −43.9 −46.7 −46.5 −46.8 −46.1
83 PMe2 (o-NMe2 C6 H4 ) 5.4326 3.0000 2.0000 3.1922 −52.2 −47.1 −46.8 −47.0 −46.4
84 PMe2 (p-tol) 5.0411 3.0000 2.0000 2.0000 −38.6 −42.2 −42.0 −42.3 −41.7
85 PMe2 (p-ClC6 H4 ) 5.4098 3.0000 2.0000 2.0000 −37.8 −43.2 −43.0 −43.3 −42.7
86 PMe2 (p-MeOC6 H4 ) 5.2842 3.0000 2.0000 2.0000 −39.1 −42.9 −42.6 −42.9 −42.4
87 PMe2 (C6 F5 ) 11.7774 3.0000 2.0000 5.1216 −47.8 −70.2 −69.9 −70.7 −69.6
88 PMe2 (o-NC5 H4 ) 6.2694 3.0000 2.1922 2.0000 −41.6 −42.6 −42.3 −42.6 −42.1
89 P(CH2 NEt2 )2 Ph 7.0171 3.0000 4.3843 6.0000 −51.3 −24.2 −23.9 −24.0 −23.5
90 PMe(CH2 OH)2 6.8779 3.0000 2.2118 0 −36.9 −37.5 −37.3 −37.6 −37.3
91 PMe(CH2 Cl)2 f 8.8185 3.0000 2.4784 0 −26.9 −38.7 −38.4 −38.9 −38.6
92 PMe(CF3 )2 33.8185 3.0000 9.3647 0 −5.8 −1.4 −0.6 −0.7 −3.0
93 PMe(CN)2 14.9258 3.1922 0 0 −81.4 −84.7 −84.4 −85.0 −84.6
94 PMeEt2 3.8390 3.0000 2.0000 0 −34.0 −32.6 −32.4 −32.6 −32.3
95 PMe(n-Pr)2 3.9646 3.0000 2.0000 2.0000 −45.0 −39.3 −39.1 −39.2 −38.8
96 PMe(t-Bu)2 4.8366 3.0000 6.0000 0 10.8 25.2 25.6 25.5 25.2
97 PMeBz2 4.6701 3.0000 2.0000 4.0000 −30.0 −47.6 −47.4 −47.9 −46.8
98 PMePh2 6.6678 3.0000 4.0000 4.0000 −28.0 −22.7 −22.4 −22.7 −22.2
99 PMe(p-tol)2 6.7432 3.0000 4.0000 4.0000 −21.0 −22.9 −22.6 −22.9 −22.4
100 PMe(p-ClC6 H4 )2 7.4806 3.0000 4.0000 4.0000 −20.2 −24.9 −24.5 −24.9 −24.4
101 P(CH2 NEt2 )Ph2 f 7.6747 3.0000 5.1922 6.0000 −27.3 −13.7 −13.4 −13.7 −13.1
102 PMe(i-Pr)(t-Bu) 4.5879 3.0000 5.0000 0 1.5 10.7 11.1 10.9 10.8
103 PMe(i-Pr)Ph 5.5034 3.0000 4.0000 2.0000 −37.9 −13.2 −12.9 −13.0 −12.9
104 PMe(CH2 CH2 Cl)Ph 5.9384 3.0000 3.0000 3.2392 −37.9 −33.4 −33.2 −33.4 −32.9
105 PMe(t-Bu)Ph 5.7523 3.0000 5.0000 2.0000 −11.2 1.2 1.6 1.3 1.5
106 PMeCyPh 5.6689 3.0000 4.0000 4.0000 −25.4 −20.0 −19.7 −20.0 −19.5
107 PMeBzPh 5.6689 3.0000 3.0000 4.0000 −30.9 −35.1 −34.9 −35.2 −34.5
108 PMe(o-BrCH2 C6 H4 )Ph 7.0205 3.0000 4.0000 5.0000 −29.8 −26.8 −26.5 −26.8 −26.2
109 P(CH2 CN)3 8.4349 3.0000 3.2882 0 −33.1 −25.4 −25.1 −25.3 −25.4
110 PEt2 (CH2 CN) 5.5377 3.0000 3.0961 0 −24.4 −20.6 −20.3 −20.5 −20.4
111 PEt2 CH(NMe2 )f 5.7700 3.0000 4.3843 4.0000 −23.6 −14.5 −14.2 −14.4 −14.0
112 PEt2 Ph 5.5034 3.0000 4.0000 2.0000 −15.1 −13.2 −12.9 −13.2 −12.9
113 PEt2 (p-FC6 H4 ) 6.2568 3.0000 4.0000 2.0000 −16.1 −15.2 −14.9 −15.2 −14.9
114 PEt2 (p-ClC6 H4 ) 5.9098 3.0000 4.0000 2.0000 −15.9 −14.3 −14.0 −14.3 −14.0
115 PEt2 (p-BrC6 H4 ) 5.8253 3.0000 4.0000 2.0000 −16.0 −14.1 −13.7 −14.1 −13.7
116 PEt2 (p-MeOC6 H4 ) 5.7842 3.0000 4.0000 2.0000 −17.6 −14.0 −13.6 −13.9 −13.6
117 PEt2 (p-NMe2 C6 H4 ) 5.6473 3.0000 4.0000 2.0000 −19.1 −13.6 −13.3 −13.6 −13.3
118 PEt2 (p-NHEtC6 H4 ) 5.6381 3.0000 4.0000 2.0000 −17.8 −13.6 −13.2 −13.5 −13.2
119 PEt2 (mesityl) 5.7626 3.0000 4.0000 4.0000 −21.9 −20.3 −20.0 −20.3 −19.7
120 PEt2 (C6 F5 ) 12.2774 3.0000 4.0000 5.1216 −23.4 −41.3 −40.9 −41.4 −40.9
121 PEt(t-Bu)2 f 5.0866 3.0000 7.0000 0 33.7 39.6 40.1 39.8 39.5
122 PEt(Cy)2 4.9201 3.0000 5.0000 4.0000 −0.6 −2.9 −2.6 −2.9 −2.4
123 PEtPh2 6.9178 3.0000 5.0000 4.0000 −12.0 −8.3 −7.9 −8.2 −7.8
124 PEt(C6 F5 )2 20.4658 3.0000 5.0000 10.2431 −44.0 −64.3 −64.0 −65.2 −63.9
125 PEt(mesityl)2 7.4361 3.0000 5.0000 8.0000 −18.1 −22.4 −22.1 −22.4 −21.5
126 P(CH2 CN)Ph2 8.3664 3.0000 5.0961 4.0000 −18.0 −10.7 −10.3 −10.6 −10.3
127 PEtCyPh 5.9189 3.0000 5.0000 4.0000 −8.1 −5.6 −5.2 −5.6 −5.1
128 P(n-Pr)3 4.2774 3.0000 3.0000 3.0000 −33.0 −28.2 −28.0 −28.2 −27.6
129 P(CH2 CH2 CN)3 4.8390 3.0000 6.0000 0 19.3 25.2 25.6 25.3 25.2
842 J. Tong et al. / Spectrochimica Acta Part A 67 (2007) 837–846

Table 1 (Continued )

No. Compound INI ε␣ ε␤ ε␥ CSEX a CSMO b CSMR c CSCV d CSCal e

130 P(n-Pr)2 (t-Bu) 5.3630 3.0000 3.0000 3.2882 −23.0 −32.1 −31.8 −32.1 −31.5
131 P(n-Pr)2 (t-Bu)f 4.7135 3.0000 5.0000 2.0000 −8.7 4.0 4.4 4.1 4.3
132 PPr(p-ClC6 H4 )2 7.7934 3.0000 5.0000 5.0000 −17.5 −13.8 −13.4 −13.8 −13.3
133 P(i-Pr)2 (CH2 CN) 6.0377 3.0000 5.0961 0 0.7 8.3 8.7 8.4 8.3
134 P(i-Pr)2 Ph 6.0034 3.0000 6.0000 2.0000 6.8 15.7 16.1 15.8 15.9
135 P(n-Pr)(t-Bu)2 5.1495 3.0000 7.0000 1.0000 26.3 36.3 36.7 36.5 36.3
136 P(n-Pr)Ph2 6.9806 3.0000 5.0000 5.0000 −17.6 −11.6 −11.3 −11.6 −11.1
137 P(n-Pr)Cy2 4.9829 3.0000 5.0000 5.0000 −7.0 −6.3 −5.9 −6.3 −5.6
138 P(i-Pr)(t-Bu)2 5.3368 3.0000 8.0000 0 45.9 54.1 54.6 54.4 53.9
139 P(i-Pr)Ph2 7.1678 3.0000 6.0000 4.0000 0.7 6.2 6.6 6.2 6.5
140 P(n-Pr)CyPh 5.9817 3.0000 5.0000 5.0000 −13.5 −8.9 −8.6 −8.9 −8.4
141 P(n-Bu)3 f 4.3219 3.0000 3.0000 3.0000 −32.3 −28.4 −28.1 −28.3 −27.8
142 P(i-Bu)3 4.4623 3.0000 3.0000 6.0000 −40.0 −38.3 −38.1 −38.3 −37.4
143 P(t-Bu)3 5.5856 3.0000 9.0000 0 61.1 68.5 69.1 68.9 68.3
144 P(n-Bu)2 (t-Bu) 4.7432 3.0000 5.0000 2.0000 −4.6 3.9 4.3 4.0 4.2
145 P(n-Bu)2 Ph 5.6587 3.0000 4.0000 4.0000 −25.8 −20.0 −19.7 −20.0 −19.4
146 P(i-Bu)2 Ph 5.7523 3.0000 4.0000 6.0000 −34.2 −26.6 −26.3 −26.6 −25.8
147 P(s-Bu)2 Ph 6.1267 3.0000 6.0000 4.0000 1.8 9.0 9.4 9.0 9.4
148 P(t-Bu)2 Bz 5.5023 3.0000 7.0000 2.0000 33.7 32.1 32.6 32.1 32.3
149 P(t-Bu)2 Ph 6.5011 3.0000 8.0000 2.0000 40.2 44.6 45.1 44.7 44.6
150 P(t-Bu)2 (p-tol) 6.5388 3.0000 8.0000 2.0000 37.0 44.5 45.0 44.7 44.5
151 P(n-Bu)(t-Bu)2 f 5.1644 3.0000 7.0000 1.0000 26.6 36.2 36.7 36.5 36.3
152 P(n-Bu)Ph2 6.9954 3.0000 5.0000 5.0000 −17.1 −11.6 −11.3 −11.6 −11.1
153 P(i-Bu)Ph2 7.0422 3.0000 5.0000 6.0000 −21.0 −15.0 −14.6 −14.9 −14.3
154 P(s-Bu)Ph2 7.2295 3.0000 6.0000 5.0000 −2.8 2.8 3.2 2.9 3.3
155 P(t-Bu)Ph2 7.4167 3.0000 7.0000 4.0000 17.2 20.6 21.1 20.7 20.9
156 P(n-pentyl)3 4.3356 3.0000 3.0000 3.0000 −34.0 −28.4 −28.1 −28.3 −27.8
157 P(cyclopentyl)3 5.3356 3.0000 6.0000 6.0000 4.7 4.7 5.1 4.7 5.4
158 P(CMe2 Et)Ph2 7.4795 3.0000 7.0000 5.0000 15.4 17.3 17.7 17.3 17.7
159 P(CMeEt2 )Ph2 7.5422 3.0000 7.0000 6.0000 11.4 13.9 14.4 14.0 14.4
160 P(n-octyl)3 4.3390 3.0000 3.0000 3.0000 −31.8 −28.4 −28.1 −28.4 −27.8
161 P(o-MeOC6H4)3 f 10.8596 3.0000 6.0000 10.0471 −37.1 −22.9 −22.6 −22.7 −22.1
162 PBz3 5.3356 3.0000 3.0000 6.0000 −10.4 −40.6 −40.4 −41.0 −39.8
163 PBzPh2 7.3332 3.0000 5.0000 6.0000 −10.4 −15.7 −15.4 −15.8 −15.1
164 PCy3 5.3356 3.0000 6.0000 6.0000 7.0 4.7 5.1 4.7 5.4
165 PCy2 Ph 6.3345 3.0000 6.0000 6.0000 2.5 2.0 2.4 2.0 2.7
166 PCyPh2 7.3333 3.0000 6.0000 6.0000 −4.4 −0.6 −0.2 −0.6 −0.1
167 PPh3 8.3322 3.0000 6.0000 6.0000 −4.7 −3.3 −2.9 −3.3 −2.8
168 P(o-FC6 H4 )3 15.1062 3.0000 6.0000 10.6824 −44.6 −36.3 −35.9 −36.1 −35.6
169 P(o-MeOC6 H4 )2 (p-MeOC6 H4 ) 10.2979 3.0000 6.0000 8.6980 −27.7 −17.1 −16.8 −17.0 −16.4
170 P(o-tol)3 8.6678 3.0000 6.0000 9.0000 −30.5 −13.7 −13.4 −13.5 −12.9
171 P(m-FC6 H4 )3 f 10.5925 3.0000 6.0000 6.0000 −6.5 −9.3 −8.9 −9.3 −8.9
172 P(m-ClC6 H4 )3 9.3288 3.0000 6.0000 6.0000 −4.4 −6.0 −5.6 −6.0 −5.5
173 P(m-tol)3 8.4452 3.0000 6.0000 6.0000 −5.7 −3.6 −3.2 −3.6 −3.1
174 P(m-MeOC6 H4 )3 9.1747 3.0000 6.0000 6.0000 −2.1 −5.5 −5.1 −5.6 −5.1
175 P(p-ClC6 H4 )3 9.5514 3.0000 6.0000 6.0000 −9.2 −6.5 −6.1 −6.5 −6.1
176 P(p-BrC6 H4 )3 9.2979 3.0000 6.0000 6.0000 −8.2 −5.9 −5.5 −5.9 −5.4
177 P(p-tol)3 8.4452 3.0000 6.0000 6.0000 −8.0 −3.6 −3.2 −3.6 −3.1
178 P(p-PrC6 H4 )3 8.4795 3.0000 6.0000 6.0000 −8.2 −3.7 −3.3 −3.7 −3.2
179 P(p-i-PrC6 H4 )3 8.5000 3.0000 6.0000 6.0000 −7.8 −3.7 −3.3 −3.7 −3.2
180 P(p-BuC6 H4 )3 8.4795 3.0000 6.0000 6.0000 −7.6 −3.7 −3.3 −3.7 −3.2
181 P(p-t-BuC6 H4 )3 f 8.5274 3.0000 6.0000 6.0000 −9.1 −3.8 −3.4 −3.8 −3.3
182 P(p-MeOC6 H4 )3 9.1747 3.0000 6.0000 6.0000 −10.8 −5.5 −5.1 −5.5 −5.1
183 P(p-SMeC6 H4 )3 8.6301 3.0000 6.0000 6.0000 −8.3 −4.1 −3.7 −4.1 −3.6
184 P(p-NO2 C6 H4 )3 12.5445 3.0000 6.0000 6.0000 5.1 −14.5 −14.1 −14.7 14.2
185 P(p-Me2 NC6 H4 )3 8.7637 3.0000 6.0000 6.0000 −11.5 −4.4 −4.0 −4.4 −4.0
186 P(2,6-F2 C6 H3 )3 21.8801 3.0000 6.0000 15.3647 −78.5 −69.3 −68.9 −68.7 −68.4
187 P(2,3,6-F3 C6 H2 )3 24.1370 3.0000 6.0000 15.3647 −78.5 −75.4 −75.0 −75.1 −74.6
188 P(2,6-(MeO)2 C6 H3 )3 13.3836 3.0000 6.0000 14.0941 −65.7 −42.6 −42.2 −41.5 −41.4
189 P(C6 F5 )3 28.6541 3.0000 6.0000 15.3647 −76.0 −87.4 −87.0 −88.7 −86.8
190 P(mesityl)3 9.1096 3.0000 6.0000 12.0000 −39.5 −24.5 −24.2 −24.0 −23.3
191 PPh2 (o-FC6 H4 )f 10.5902 3.0000 6.0000 7.5608 −19.8 −14.3 −13.9 −14.3 −13.7
192 PPh2 (o-ClC6 H4 ) 9.5502 3.0000 6.0000 7.2392 −10.9 −10.5 −10.1 −10.5 −9.9
193 PPh2 (o-OHC6 H4 ) 9.1187 3.0000 6.0000 7.1059 −18.1 −8.9 −8.5 −8.8 −8.3
194 PPh2 (o-tol) 8.4441 3.0000 6.0000 7.0000 −13.0 −6.8 −6.4 −6.7 −6.2
J. Tong et al. / Spectrochimica Acta Part A 67 (2007) 837–846 843

Table 1 (Continued )

No. Compound INI ε␣ ε␤ ε␥ CSEX a CSMO b CSMR c CSCV d CSCal e

195 PPh2 (o-MeOC6 H4 ) 9.1747 3.0000 6.0000 7.3490 −16.0 −9.8 −9.5 −9.8 −9.2
196 PPh2 (o-EtOC6 H4 ) 9.1884 3.0000 6.0000 7.3490 −15.2 −9.9 −9.5 −9.8 −9.3
197 PPh2 (o-NMe2 C6 H4 ) 8.7614 3.0000 6.0000 7.1922 −13.5 −8.2 −7.9 −8.2 −7.6
198 PPh2 (m-FC6 H4 ) 9.0856 3.0000 6.0000 6.0000 −10.9 −5.3 −4.9 −5.3 −4.8
199 PPh2 (m-CNC6 H4 ) 8.5845 3.0000 6.0000 6.0000 −8.3 −4.0 −3.6 −3.9 −3.5
200 PPh2 (p-ClC6 H4 ) 8.7386 3.0000 6.0000 6.0000 −6.9 −4.4 −4.0 −4.4 −3.9
201 PPh2 (p-BrC6 H4 )f 8.6541 3.0000 6.0000 6.0000 −4.8 −4.2 −3.8 −4.1 −3.7
202 PPh2 (p-MeOC6 H4 ) 8.6130 3.0000 6.0000 6.0000 −7.0 −4.0 −3.6 −4.0 −3.5
203 PPh2 (p-NMe2 C6 H4 ) 8.4760 3.0000 6.0000 6.0000 −7.0 −3.7 −3.3 −3.7 −3.2
204 PPh2 (p-BuC6 H4 ) 8.3813 3.0000 6.0000 6.0000 −6.5 −3.4 −3.0 −3.4 −2.9
205 P(CH2 CH2 CH CH2 )3 4.4212 3.0000 3.0000 3.0000 −30.2 −28.6 −28.4 −28.6 −28.0
206 PPh(o-FC6 H4 )2 12.8482 3.0000 6.0000 9.1216 −32.5 −25.3 −24.9 −25.2 −24.7
207 PPh(o-ClC6 H4 )2 10.7683 3.0000 6.0000 8.4784 −18.8 −17.7 −17.3 −17.7 −17.0
208 PPh(o-MeOC6 H4 )2 10.0171 3.0000 6.0000 8.6980 −27.2 −16.4 −16.0 −16.3 −15.7
209 PPh(C6 F5 )2 21.8801 3.0000 6.0000 12.2431 −48.7 −59.4 −59.0 −59.9 −58.8
210 P(o-tol)2 (p-tol) 8.5936 3.0000 6.0000 8.0000 −22.1 −10.4 −10.0 −10.2 −9.6
211 P(p-tol)2 (p-ClC6 H4 )f 8.8139 3.0000 6.0000 6.0000 −8.2 −4.6 −4.2 −4.6 −4.1
212 P(p-tol)2 (p-MeOC6 H4 ) 8.6884 3.0000 6.0000 6.0000 −9.2 −4.2 −3.8 −4.2 −3.7
213 P(p-ClC6 H4 )(p-MeOC6 H4 )2 9.3002 3.0000 6.0000 6.0000 −8.4 −5.9 −5.5 −5.9 −5.4
214 P(p-BrC6 H4 )(p-MeOC6 H4 )2 9.2158 3.0000 6.0000 6.0000 −8.6 −5.7 −5.3 −5.6 −5.2
215 P(p-tol)(p-MeOC6 H4 )2 8.9315 3.0000 6.0000 6.0000 −10.0 −4.9 −4.5 −4.9 −4.4
216 PEt3 4.0890 3.0000 3.0000 0 −20.4 −18.2 −17.9 −18.1 −17.9
217 P(CHOHCCl3 )3 15.5616 3.0000 6.3176 11.1529 18.0 −34.2 −33.8 −35.5 −33.5
218 PMe2 (COMe) 8.7237 3.0000 2.3490 0 −19.7 −40.4 −40.1 −40.9 −40.3
219 PMe2 (CN) 9.1324 3.0961 0 0 −63.0 −73.1 −72.9 −73.6 −72.8
220 P(CN)2 (C6 F5 ) 23.3642 3.1922 2.0000 5.1216 −121.3 −93.3 −93.0 −90.8 −93.3
221 PMe(CH2 CH2 SH)2 f 4.1107 3.0000 2.0000 1.8745 −42.3 −39.3 −39.1 −39.3 −38.8
222 PMe(C6 F5 )2 20.2158 3.0000 4.0000 10.2431 −52.2 −78.8 −78.4 −80.1 −78.2
223 PMeEtPh 5.2534 3.0000 3.0000 2.0000 −32.8 −27.7 −27.4 −27.6 −27.2
224 PMe(n-Pr)Ph 5.3162 3.0000 3.0000 3.0000 −37.9 −31.0 −30.7 −31.0 −30.5
225 PMe(CH2 CH2 CH2 Cl)Ph 5.4874 3.0000 3.0000 3.0000 −36.3 −31.5 −31.2 −31.4 −30.9
226 PMe(CH CH2 )Ph 5.7808 3.0000 3.0000 2.0000 −18.2 −29.1 −28.8 −29.2 −28.7
227 PEt2 (t-Bu) 4.5879 3.0000 5.0000 0 −6.6 10.7 11.1 11.0 10.8
228 P(CHOHCH3 )2 Ph 9.0422 3.0000 6.2118 2.0000 −12.0 10.8 11.2 11.0 10.8
229 P(CHOHCCl3 )2 Ph 13.1518 3.0000 6.2118 9.4353 −10.0 −23.9 −23.5 −24.1 −23.3
230 P(CH2 CH2 NH2 )2 Ph 5.9030 3.0000 4.0000 4.3844 −25.6 −21.9 −21.6 −21.9 −21.3
231 P(CH2 CN)2 Phf 8.4007 3.0000 4.1922 2.0000 −28.9 −18.1 −17.7 −18.0 −17.9
232 PEt(CH CH2 )2 5.1438 3.0000 3.0000 0 −20.8 −21.0 −20.7 −21.0 −20.8
233 P(CH2 CH CH2 )3 4.6712 3.0000 3.0000 3.0000 −34.5 −29.3 −29.0 −29.2 −28.7
234 P(n-Pr)2 Ph 5.6290 3.0000 4.0000 4.0000 −27.7 −19.9 −19.6 −19.9 −19.4
235 P(i-Pr)2 (CN) 10.1324 3.0961 4.0000 0 −7.5 −15.3 −14.9 −15.5 −15.4
236 P(i-Pr)2 (CH2 CH2 CH2 Cl) 4.8231 3.0000 5.0000 1.0000 1.4 6.9 7.3 7.0 7.1
237 P(i-Pr)2 CO2 Me 11.9167 3.0000 6.6980 1.0000 16.9 13.6 14.1 13.5 13.4
238 P(i-Pr)2 COCF3 14.8037 3.0000 6.3490 4.6824 41.2 −11.1 −10.6 −11.7 −11.1
239 P(i-Pr)2 COCH2 F 11.4167 3.0000 6.3490 1.5608 32.0 7.9 8.4 7.5 7.7
240 P(i-Pr)2 COMe 9.7237 3.0000 6.3490 0 38.7 17.4 17.9 16.9 17.1
241 P(i-Pr)2 CO-t-Buf 9.9726 3.0000 6.3490 3.0000 15.1 7.2 7.6 7.1 7.2
242 P(i-Pr)2 COPh 10.2785 3.0000 6.3490 2.0000 26.5 9.5 10.0 9.3 9.5
243 P(i-Pr)2 CO(p-BrC6 H4 ) 10.3858 3.0000 6.3490 2.0000 26.1 9.2 9.7 9.0 9.2
244 P(CH2 CH2 CN)2 Ph 6.3527 3.0000 4.0000 4.1922 −23.8 −22.5 −22.2 −22.5 −21.9
245 P(CH2 CH2 CH2 CH2 Cl)Ph2 7.0388 3.0000 5.0000 5.0000 −17.9 −11.8 −11.4 −11.7 −11.2
246 P(o-NC5 H4 )3 12.1301 3.0000 6.5765 6.0000 −1.3 −4.7 −4.3 −4.8 −4.4
247 P(i-Pr)(t-Bu)(CH2 CH CH2 ) 5.0320 3.0000 6.0000 1.0000 14.4 21.5 21.9 21.6 21.6
248 P(i-Pr)BzCOMe 9.8893 3.0000 5.3490 2.0000 27.9 −4.5 −4.1 −4.8 −4.5
249 P(t-Bu)2 (CH2 COPh) 6.5719 3.0000 7.0000 2.3490 30.6 28.2 28.6 28.1 28.3
250 P(n-Bu)(n-octyl)2 4.3333 3.0000 3.0000 3.0000 −33.3 −28.4 −28.1 −28.3 −27.8
251 P(t-Bu)(CH2 CH CH2 )2 f 4.9760 3.0000 5.0000 2.0000 −6.0 3.3 3.7 3.4 3.6
252 P(t-Bu)(p-tol)2 7.4920 3.0000 7.0000 4.0000 15.2 20.4 20.9 20.5 20.7
253 P(t-Bu)BzCO2 Me 12.3311 3.0000 6.6980 3.0000 19.5 6.1 6.6 6.0 6.1
254 P(t-Bu)BzCOTf 13.8790 3.0000 6.3608 5.6980 36.1 −11.7 −11.2 −12.1 −11.5
255 P(t-Bu)PhCOMe 13.1370 3.0000 7.3490 2.0000 40.8 17.0 17.5 16.5 16.7
256 P(t-Bu)PhCOCF3 16.2169 3.0000 7.3490 6.6824 39.2 −6.1 −5.6 −6.8 −6.0
257 P(neopentyl)Ph2 7.1050 3.0000 5.0000 7.0000 −23.9 −18.3 −18.0 −18.3 −17.6
258 P(cyclopentyl)2 Ph 6.3345 3.0000 6.0000 6.0000 1.6 2.0 2.4 2.1 2.7
259 P(cyclopentyl)Ph2 7.3333 3.0000 6.0000 6.0000 −3.9 −0.6 −0.2 −0.6 −0.1
844 J. Tong et al. / Spectrochimica Acta Part A 67 (2007) 837–846

Table 1 (Continued )

No. Compound INI ε␣ ε␤ ε␥ CSEX a CSMO b CSMR c CSCV d CSCal e

260 P(o-MeSC6 H4 )3 9.2226 3.0000 6.0000 9.0353 −30.2 −15.3 −15.0 −15.1 −14.5
261 P(n-octyl)(CH2 CH2 CN)2 f 5.0217 3.0000 3.0000 3.1922 −25.7 −30.8 −30.6 −30.9 −30.3
262 PBz2 Ph 6.3345 3.0000 4.0000 6.0000 −12.1 −28.2 −27.9 −28.3 −27.4
263 PBz(CH2 CH CH2 )Ph 6.1130 3.0000 4.0000 5.0000 −20.7 −24.4 −24.1 −24.4 −23.8
264 P(CHOHPh)2 Ph 9.8733 3.0000 6.2118 6.0000 −6.0 −4.2 −3.8 −4.2 −3.8
265 PCy2 (CH2 CH2 Cl) 5.6050 3.0000 5.0000 5.2392 −6.2 −8.7 −8.4 −8.7 −8.1
266 PCy2 COCCl3 12.7945 3.0000 6.3490 7.7176 20.5 −15.4 −15.0 −15.8 −14.9
267 PCy2 COCHCl2 11.8813 3.0000 6.3490 6.4784 26.4 −9.0 −8.6 −9.3 −8.7
268 PCy2 COCH2 Cl 10.9680 3.0000 6.3490 5.2392 29.1 −2.6 −2.2 −2.8 −2.4
269 P(m-hexylC6 H4 )3 8.4829 3.0000 6.0000 6.0000 −7.7 −3.7 −3.3 −3.7 −3.2
270 P(m-CF3 C6 H4 )3 10.1370 3.0000 6.0000 6.0000 −4.3 −8.1 −7.7 −8.1 −7.7
271 P(p-CF3 C6 H4 )3 f 10.1370 3.0000 6.0000 6.0000 −7.0 −8.1 −7.7 −8.1 −7.7
272 P(2,3-(MeO)2 C6 H3 )3 11.7021 3.0000 6.0000 10.0471 −40.8 −25.2 −24.8 −24.9 −24.4
273 P(2,3-(EtO)2 C6 H3 )3 11.7568 3.0000 6.0000 10.0471 −64.6 −25.3 −25.0 −24.7 −24.5
274 P(o-CF3 C6 H4 )3 13.7466 3.0000 6.0000 9.0000 −18.4 −27.3 −26.9 −27.4 −26.7
275 P(CH2 CH2 CN)Ph2 7.3425 3.0000 5.0000 5.0961 −17.6 −12.9 −12.5 −12.9 −12.3
276 PPh2 (o-NEt2 C6 H4 ) 8.7797 3.0000 6.0000 7.1922 −14.1 −8.3 −7.9 −8.2 −7.7
277 PPh2 (m-CF3 C6 H4 ) 8.9338 3.0000 6.0000 6.0000 −10.9 −4.9 −4.5 −4.9 −4.4
278 PPh(CH2 CH CH2 )2 5.8916 3.0000 4.0000 4.0000 −27.5 −20.6 −20.3 −20.6 −20.1
279 PPh(CH2 NEt2 )2 7.0171 3.0000 4.3843 6.0000 −51.3 −24.2 −23.9 −24.0 −23.5
280 PPh(o-tol)2 8.5559 3.0000 6.0000 9.0000 −21.4 −13.4 −13.1 −13.3 −12.6
281 PPh(o-CF3 C6 H4 )2 f 11.9418 3.0000 6.0000 9.0000 −14.5 −22.5 −22.1 −22.6 −21.8
282 PPh(p-ClC6 H4 )2 9.1450 3.0000 6.0000 6.0000 −8.0 −5.5 −5.1 −5.4 −5.0
283 PPh(p-tol)2 8.4075 3.0000 6.0000 6.0000 −7.0 −3.5 −3.1 −3.5 −3.0
284 P(m-ClC6 H4 )2 (p-CF3 C6 H4 ) 9.5982 3.0000 6.0000 6.0000 −7.5 −6.7 −6.3 −6.7 −6.2
285 P(p-MeOC6 H4 )2 (p-NMe2 C6 H4 ) 9.0377 3.0000 6.0000 6.0000 −9.5 −5.2 −4.8 −5.1 −4.7
286 P(m-ClC6 H4 )(p-CF3 C6 H4 )2 9.8676 3.0000 6.0000 6.0000 −6.3 −7.4 −7.0 −7.4 −7.0
287 P(o-MeSC6 H4 )2 (p-MeOC6 H4 )* 9.2066 3.0000 6.0000 9.0353 −23.1 −15.3 −14.9 −15.2 −14.5
288 P(o-MeSC6 H4 )2 (p-MeSC6 H4 )* 9.0251 3.0000 6.0000 8.0235 −21.1 −11.6 −11.2 −11.5 −10.9
289 P(o-MeOC6 H4 )2 (p-MeSC6 H4 )* 10.1164 3.0000 6.0000 8.6980 −25.9 −16.7 −16.3 −16.5 −15.9
290 P(o-NC5 H4 )2 (p-MeOC6 H4 )* 11.1450 3.0000 6.3843 6.0000 −2.3 −5.0 −4.6 −5.0 −4.6
291 P(o-NC5 H4 )2 (p-MeSC6 H4 )f,* 10.9635 3.0000 6.3843 6.0000 −1.6 −4.5 −4.1 −4.5 −4.2
a All values were taken from Ref. [29], except those marked with asterisks, which were taken from Ref. [30].
b Calculated values by MLR model utilized 291 samples.
c Calculated values by MLR model utilized 261 training samples and 30 prediction samples.
d Calculated value of leave-one-out cross-validation by MLR model utilized 291 samples.
e Calculated value by PLS model.
f Prediction set members.

3.3. Physical significance of MLR model coefficients on 31 P NMR chemical shifts, that is, the differently positional
atoms of the phosphorus atom give rise to shielding or deshield-
As we know, phosphines are considered as derivatives of PH3 , ing effect on the phosphorus nucleus. As for ␣,␤-substituents of
the ability of non-hydrogen atoms offer electronics more than phosphorus nucleus, owing to hyperconjugation and homocon-
hydrogen atom. Thus the substitution of hydrogen atom by non- jugation effect, the electronic density of phosphorus atom will
hydrogen atoms leads to the electronic cloud density increases decreased, therefore, 31 P NMR chemical shifts value increased,
on phosphorus atom, and value of INI also increases. The results the positive coefficient of ε␣ and ε␤ indicates their favorable
give rise to the more upfield resonance, that is, 31 P NMR chemi- contribution for 31 P NMR chemical shifts. However, the coeffi-
cal shifts value decreased. The negative coefficient of INI in the cient of the indicator parameter ε␥ is negative meaning, thereby,
above Eq. (6) indicates that 31 P NMR chemical shifts are directly that the presence of ␥-substituents has negative effect on the
(linearly) related to the magnitude of INI value. In addition, the exhibition of 31 P NMR chemical shifts. Another the magni-
presence of attached and nearby atoms have a profound effect tude of coefficient reflected structure parameters, that is, INI,

Table 2
Analyses of variables by stepwise multiple regression
No. a0 a1 a2 a3 a4 R2 R rms F Q2 Q rmsCV FCV

1 −173.9501 − 52.8950 − − 0.6236 0.7897 26.7689 478.8934 0.6189 0.7867 26.9384 469.2581
2 −175.2675 − 37.3884 9.6458 − 0.7667 0.8756 21.1144 473.1219 0.7585 0.8709 21.4799 452.3026
3 −174.4448 −3.1142 38.9954 13.9258 − 0.8608 0.9278 16.3310 592.0602 0.8563 0.9254 16.5981 570.1012
4 −174.0197 −2.6724 40.4755 15.1141 −3.1858 0.8985 0.9479 13.9792 632.4384 0.8918 0.9444 14.4257 589.5331
J. Tong et al. / Spectrochimica Acta Part A 67 (2007) 837–846 845

PLS analysis. Cross-validation was done by the leave-one-out


procedure (LOO).
The selected variables were modeled by PLS, the first three
components explained 94.66% and 94.07% variance of Y and
cross-validation variance of Y, respectively. From loading plot
of the first two components (Fig. 2), it can be seen that the first
principal component is mainly related with ε␤ and ε␥ , the second
principal component is mainly related with INI and ε␣ .
The corresponding results of external validation, Qext were
0.9599. This PLS model was then employed to calculate 31 P
NMR chemical shifts, given in Table 1.

4. Conclusion

It can be seen that the correlation with Eq. (6) of 31 P NMR


chemical shifts of phosphine compounds is simple to calculate.
The correlation coefficient is R = 0.9479, and the expression is
suitable for calculate the 31 P NMR chemical shifts of phos-
phine compounds (contains primary, secondary, and tertiary
phosphines, at the same time the phosphines are very different
Fig. 1. Plot of experimental vs. calculated 31 P NMR chemical shifts of 291
phosphorus atoms for MO (a), MR (b), CV (c) by MLR model. (a) Utilized 291
from their steric and electronic characteristics, since they have
samples to built MLR model; (b) utilized 261 training samples and 30 prediction substituents with several heteroatoms, O, N, F, Cl, Br, and S, and
samples to built MLR model; (c) leave-one-out cross-validation by MLR model different functionalities) in a wider range of phosphorus atoms.
utilized 291 samples. In addition, Eq. (6) described a new, simple, efficient method
for calculating 31 P NMR chemical shifts of phosphines. From
ε␣ , ε␤ and ε␥ have different contribution for 31 P NMR chemical the aforementioned results we conclude that INI in combination
shifts. with stereoscopic effect parameters εi can be used successfully
for modeling 31 P NMR chemical shifts of phosphines.
3.4. Partial least square regression
Acknowledgments
Partial least square (PLS) is the most used latent regression
method for relating two data matrices, X and Y, by a linear mul- Financial supports from both the Industry Innovation Founda-
tivariate model. Compared to those traditional methods, PLS tion of Shanxi Province (2006031204) and State Key Laboratory
can analyze some data sets with many, noisy, collinear, and even of Chemo/Biosensing and Chemometrics foundation (05-12-1)
incomplete variables in both X and Y. PLS has the desirable prop- are gratefully acknowledged.
erty that the precision of the model parameters improves with
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