The interactions between the sterically demanding trimesitylphosphine oxide and trimesityphosphine with scandium and selected lanthanide ions

Article abstract of DOI:10.1016/j.molstruc.2016.01.073

The reactions between lanthanide nitrates, Ln(NO₃)₃ and scandium and lanthanide trifluoromethane sulfonates, Ln(Tf)₃ with trimesitylphosphine oxide, Mes₃PO show that coordination to the metal ions does not lead to crystalline complexes. Investigation of the reactions by 31-P NMR spectroscopy shows that weak complexes are formed in solution. The crystal structures of Mes₃PO·0.5CH₃CN (1) and [Mes₃PO]₃H₃O·2CH₃CN·Tf (2), formed in the reaction between ScTf₃ and Mes₃PO, are reported. Trimesitylphosphine, Mes₃P, is protonated by scandium and lanthanide trifluoromethane sulfonates and lanthanide nitrates in CD₃CN and the structure of [Mes₃PH]Cl·HCl·2H₂O (3) is reported.

Full text of DOI:10.1016/j.molstruc.2016.01.073

Journal of Molecular Structure 1111 (2016) 180e184
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: http://www.elsevier.com/locate/molstruc
The interactions between the sterically demanding
trimesitylphosphine oxide and trimesityphosphine with scandium
and selected lanthanide ions
,
Andrew W.G. Platt a *, Kuldip Singh b
a School of Sciences, Staffordshire University, Leek Road, Stoke on Trent, ST4 2DF, UK
b Chemistry Department, The University, Leicester, LE1 7RH, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
The reactions between lanthanide nitrates, Ln(NO3)3 and scandium and lanthanide trifluoromethane
sulfonates, Ln(Tf)3 with trimesitylphosphine oxide, Mes3PO show that coordination to the metal ions
does not lead to crystalline complexes. Investigation of the reactions by 31-P NMR spectroscopy shows
that weak complexes are formed in solution. The crystal structures of Mes3PO$0.5CH3CN (1) and
[Mes3PO]3H3O$2CH3CN$Tf (2), formed in the reaction between ScTf3 and Mes3PO, are reported. Tri-
mesitylphosphine, Mes3P, is protonated by scandium and lanthanide trifluoromethane sulfonates and
lanthanide nitrates in CD3CN and the structure of [Mes3PH]Cl$HCl$2H2O (3) is reported.
© 2016 Elsevier B.V. All rights reserved.
Received 12 October 2015
Received in revised form
26 January 2016
Accepted 26 January 2016
Available online 1 February 2016
Keywords:
Phosphine oxide
Lanthanide
Scandium solution NMR
X-ray crystal structure
1. Introduction
sterically demanding trimesitylphosphine oxide, for which the
cone angle of the parent phosphine is 212ꢀ [9].
The coordination chemistry of phosphine oxides with lantha-
nide ions has attracted interest for a number of years because of the
potential the complexes have in a variety of applications [1,2].
Complexes of lanthanide nitrates have been studied in some
detail in the solvent extraction separation of lanthanide from ac-
tinides carried out in nitric acid solutions [3e5]. We have previ-
ously studied the effect on structures and solution properties of
increasing the size of the R group in R3PO where we found that
solid state structures and solution properties depend on a balance
between steric and electronic effects of the phosphine oxides and
the size of the lanthanide ions [6e8]. Cone angles, are not available
for phosphine oxides, and as a result we have used the cone angles
of the parent phosphine [9] as a proxy for the steric demands of the
oxides. Previous studies on trialkyl phosphine oxides R3PO (R ¼ Et
[6], iBu [7], cyclohexyl [10] and tBu [8]) have shown that significant
differences in the properties of the lanthanide nitrate complexes
result with changes in the steric and electronic properties of the
ligands.
Lanthanide ions do not form complexes with soft donors such as
phosphines in the presence of competition from hard donor ligands
such as water. We have previously found that sterically crowded
phosphine oxides are able to hydrogen bond to lanthanide-
coordinated water molecules [11,12]. Theoretical studies of
hydrogen bonding between phosphines and a variety of hydrogen
donors have indicated that such bonding can give rise to stable
complexes [13e15] and an HFePH3 dimer has been identified in the
gas phase [16]. In view of this we have conducted a brief investi-
gation into the interaction of the sterically demanding Mes3P with
hydrated lanthanide salts to investigate whether hydrogen bonding
to coordinated water occurred.
2. Results and discussion
2.1. Synthesis and solid state structures
Attempted synthesis of complexes of Mes3PO with representa-
tive lanthanide nitrates across the series (Ln ¼ Pr, Nd, Gd, Ho, Er, Lu)
was carried out in ethanol solution. The phosphine oxide is poorly
soluble in warm ethanol but on addition of solutions of lanthanide
nitrates clear solutions were obtained which implied that
We have extended our studies to include the more highly
* Corresponding author.
E-mail address: a.platt@staffs.ac.uk (A.W.G. Platt).
http://dx.doi.org/10.1016/j.molstruc.2016.01.073
0022-2860/© 2016 Elsevier B.V. All rights reserved.

A.W.G. Platt, K. Singh / Journal of Molecular Structure 1111 (2016) 180e184
181
interaction with the metal had taken place. Attempts to obtain
crystalline materials from these reactions by slow evaporation,
cooling to ꢁ30 ꢀC or slow diffusion with diethylether or toluene
followed by cooling were not successful. The reactions led to either
recovery of unreacted Mes3PO, no solid materials or to the forma-
tion of oils. The reason for the apparent lack of coordination with
Ln(NO3)3 is probably a combination of the high affinity of lantha-
nide ions for nitrate and the increased steric demands of the ligand
limiting access of the phosphoryl oxygen to the coordination sites
on the metal.
Clearly there is some interaction between Mes3PO and the
lanthanide nitrates in solution, but this does not result in the for-
mation of complexes which are sufficiently stable to permit isola-
tion. The reactions of lanthanide and scandium trifluoromethane
sulfonates (triflates) were examined as the triflate ion has a low
coordinating ability and might thus lead to a less crowded coor-
dination environment around the metal. In reactions with LnTf3
Ln ¼ (Ln ¼ La, Nd, Eu, Er, Lu) in ethanol the initial suspensions of
Mes3PO cleared on addition of the lanthanide salt, again implying
some complex formation. The reaction mixtures, however, failed to
yield characterisable materials.
shows that, compared to Ph3PO, reduction in steric strain by
widening of the CePeC angle has the effect of making the methyl
groups effectively shield the phosphoryl oxygen and this probably
limits the availability of the P]O group to coordinate to the
lanthanide ion, where the environment around the metal will
already contain coordinated nitrate ions and/or water molecules.
The reaction with scandium triflate in CH3CN did produce
crystalline material which was suitable for x-ray diffraction study.
The solid does not, however, contain scandium but is
[Mes3PO]3H3Oþ CF3SO3ꢁ.2CH3CN (2). The hydronium ions are
formed are almost certainly by acid hydrolysis of hydrated Sc3þ. The
structure is shown in Fig. 2 and details of the data collection and
refinement are included in Table 1. Three Mes3PO molecules are
coordinated to H3Oþ via hydrogen bonding and the CH3CN and
triflate ions are not involved in hydrogen bonding interactions. The
P]O bonds are slightly longer (average 1.493 Å) than in Mes3PO as
expected on coordination to a positively charged centre. Larger
increases in bond distances in similar structures such as Ph3PO$HBr
(1.550 Å) [15] and Ph3PO$HNO3 (1.499 Å) [16] are probably due to
the proton being coordinated to one phosphine oxide rather than
three as in this study.
In order to assess the steric congestion around the oxygen in
Trimesitylphosphine oxide is bulkier than trialkylphosphine
t
t
trimesitylphosphine oxide the crystal structure of Mes3
oxides such as Bu3PO (the cone angle Bu3P is 182ꢀ) which forms
only 1:2 complexes with lanthanide nitrates [8]. Trimes-
itylphosphine itself forms complexes with a number of metals and
coordination compounds with Hg [17], Ag [18], Pt [19] and Au [20]
have been characterised. The inability of Mes3PO to form stable
complexes might thus be considered to be surprising as the cone
angle of the oxide will certainly be lower than that of the phos-
phine. A comparison of some of the parameters which might be
relevant to their relative coordinating ability are given in Table 3.
The approach of Mes3PO to the metal centre will be restricted by
steric interaction with the methyl groups. The proximity of the
methyls to the coordinating atoms indicates that the environments
in Mes3P and Mes3PO are similar with P … O and C … O distances
relatively short. Although the distances could be considered as
indicative of hydrogen bonding (C … O average in Mes3PO is 2.89 Å
compared to a sum of Van der Waals radii for C and O of 3.2 Å and C
… P average in Mes3P is 2.72 Å compared to a sum of Van der Waals
radii for P and C of 3.5 Å), it is more likely that these distances are
imposed by the geometrical constraints of the molecules [21].
The differences in coordinating ability probably lies in the strong
hydration of the lanthanide and scandium ions which combines
with the steric congestion of the ligand to make coordination
impossible under the conditions employed. In addition the metal
ions coordinated to Mes3P are likely to be less strongly solvated (for
example using CH2Cl2/THF as the reaction medium) and hence the
effective size of the metal ions will be lower than hydrated
lanthanide or scandium ions.
-
PO$0.5CH3CN (1) was determined. The structure is shown in Fig. 1
details of the data collection and refinement are given in Table 1
and selected bond distances and angles in Table 2. The compound
crystallises with two Mes3PO molecules and one CH3CN in the unit
cell. There are no close contacts between the acetonitrile and the
phosphine oxide. Comparison of this structure with Ph3PO, which
forms stable complexes with all simple lanthanide salts, indicates
that the structure of Mes3PO changes to reduce steric interactions
between the methyl groups and in doing so increases the crowding
of the environment around the O-atom, as described below. The P]
O bond distance is 1.486 Å which is very similar to those reported
for Ph3PO, for example 1.483 [13] and 1.487 [14]. The CePeC angles
widen to reduce steric interactions between the methyl groups in
Mes3PO with an average of 110.2ꢀ compared to 106.4ꢀ in Ph3PO.
There is also a significant increase in the PeC bond distance
compared with Ph3PO from 1.800 Å to 1.828 Å which will further
reduce steric crowding between the methyl groups. The structure
2.2. Solution NMR investigation
Given that there is clearly some interaction between the
lanthanide ions and Mes3PO several lanthanide triflate/Mes3PO
systems were investigated by 31-P NMR spectroscopy.
The results are shown in Table 4. The absence of any large co-
ordination shifts with the paramagnetic lanthanide ions indicates
that there is no direct interaction between the phosphine oxide and
the metal. However, the lines are broad and show a significant
temperature dependence of the chemical shifts which whilst
smaller than that observed for LneO]P systems, is an order of
magnitude greater than that of free Mes3PO. We recently reported
the structures of [Ln(H2O)5(Cy3PO)2]$2Cy3PO$3X (X ¼ Cl, Br) [11,12]
where Cy ¼ cyclohexyl, C6H11 in which the Cy3PO are either directly
bonded to the metal ion or through hydrogen bonding to the
Fig. 1. The structure of Mes3PO$CH3CN The acetonitrile molecule is omitted for clarity.

182
A.W.G. Platt, K. Singh / Journal of Molecular Structure 1111 (2016) 180e184
Table 1
Data collection and refinement for (1) and (2).
Mes3PO 0.5CH3CN
C56 H69 N O2 P2
850.06
[Mes3PO]3H3O$CF3SO3
C86 H107 F3 N2 O7 P3 S
1462.71
Empirical formula
Formula weight
Temperature
150(2) K
150(2) K
Wavelength
Crystal system
Space group
0.71073 Å
Triclinic
P-1
0.71073 Å
Triclinic
P-1
Unit cell dimensions
a ¼ 8.101(5) Å
a
¼ 75.593(11)ꢀ
a ¼ 16.176(4) Å
b ¼ 16.621(4) Å
c ¼ 17.233(4) Å
3948.1(17) Å3
2
a
b
g
¼ 105.682(5)ꢀ
¼ 106.410(6)ꢀ
¼ 106.253(5)ꢀ
b ¼ 16.449(10) Å
c ¼ 19.055(12) Å
2410(3) Å3
2
b
g
¼ 83.298(12)ꢀ
¼ 79.329(13)ꢀ
Volume
Z
Density (calculated)
Absorption coefficient
F(000)
Crystal size
Theta range for data collection
Index ranges
Reflections collected
Independent reflections
Completeness to theta ¼ 26.00ꢀ
Absorption correction
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2sigma(I)]
R indices (all data)
Largest diff. peak and hole
1.171 Mg/m3
0.132 mmꢁ1
916
1.230 Mg/m3
0.164 mmꢁ1
1562
0.35 ꢂ 0.23 ꢂ 0.15 mm3
0.25 ꢂ 0.20 ꢂ 0.18 mm3
1.89e26.00ꢀ
1.38e25.00ꢀ
ꢁ19 ꢃ h ꢃ 13, ꢁ19 ꢃ k ꢃ 19, ꢁ20 ꢃ l ꢃ 20
18,854
ꢁ19 ꢃ h ꢃ 13, ꢁ19 ꢃ k ꢃ 19, ꢁ20 ꢃ l ꢃ 20
19,947
9325 [R(int) ¼ 0.0682]
13,161 [R(int) ¼ 0.0960]
98.8%
94.6%
Empirical
Empirical
0.981 and 0.762
0.862 and 0.548
Full-matrix least-squares on F2
9325/0/569
Full-matrix least-squares on F2
13161/0/948
0.932
0.839
R1 ¼ 0.0606, wR2 ¼ 0.1203
R1 ¼ 0.0978, wR2 ¼ 0.1329
0.367 and ꢁ0.441 e.Åꢁ3
R1 ¼ 0.0818, wR2 ¼ 0.1372
R1 ¼ 0.1951, wR2 ¼ 0.1730
0.403 and ꢁ0.401 e.Åꢁ3
Table 2
Selected bond distances and angles for (1) and (2).
1
2
P(1)eO(1)
P(1A)eO(1A)
P(1B)eO(1B)
P(1)eC(1)
P(1A)eC(1A)
P(1B)eC(1B)
P(1)eC(10)
P(1A)eC(10A)
P(1B)eC(10B)
P(1)eC(19)
P(1A)eC(19A)
P(1B)eC(19B)
O(1)eP(1)eC(1)
O(1A)eP(1A)eC(1A)
O(1B)eP(1B)eC(1B)
O(1)eP(1)eC(10)
O(1A)eP(1A)eC(10A)
O(1B)eP(1B)eC(10B)
O(1)eP(1)eC(19)
O(1A)eP(1A)eC(19A)
O(1B)eP(1B)eC(19B)
C(1)eP(1)eC(10)
C(1A)eP(1A)eC(10A)
C(1B)eP(1B)eC(10B)
C(1)eP(1)eC(19)
C(1A)eP(1A)eC(19A)
C(1B)eP(1B)eC(19B)
C(10)eP(1)eC(19)
C(10A)eP(1A)eC(19A)
C(10B)eP(1B)eC(19B)
1.4858(18)
1.4858(19)
1.492(4)
1.500(4)
1.490(3)
1.815(6)
1.833(5)
1.843(6)
1.808(6)
1.831(6)
1.799(6)
1.831(6)
1.812(6)
1.821(6)
107.0(2)
108.2(2)
108.4(2)
108.6(2)
108.7(2)
107.9(2)
107.9(2)
107.3(2)
109.2(2)
113.5(3)
108.3(3)
113.0(3)
1.831(3)
1.826(3)
1.826(3)
1.831(3)
1.825(3)
1.828(3)
107.65(12)
108.94(11)
109.86(11)
108.02(12)
108.60(11)
108.94(11)
108.92(12)
111.10(11)
Fig. 2. The structure of [Mes3PO]3H3O]þ CF3SO3ꢁ hydrogen atoms and acetonitrile are
omitted for clarity. The dashed lines represent hydrogen bonds.
111.07(12)
108.94(11)
112.9(£0
113.3(3)
106.9(3)
113.0(3)
111.0(3)
111.5(3)
110.69(12)
110.06(11)
interesting that the temperature dependence in the Mes3PO/Ln3þ
systems is opposite of that found for 31-P shift for phosphine ox-
ides directly bonded to lanthanides [7,8], but the same as for
phosphine oxides hydrogen bonded to lanthanide coordinated
water molecules. In the absence of crystallographic data from iso-
lated compounds it is not possible to be certain of the nature of this
interaction, but hydrogen bonding to the coordinated water mol-
ecules, as previously observed with other sterically crowded
phosphine oxides [11,12] seems reasonable.
coordinated water molecules. In these systems the temperature
dependence of the 31-P NMR shifts depends on whether the Cy3PO
is directly bonded to the metal for example þ0.7 ppmKꢁ1 for P]
OeEu and ꢁ0.1 ppmKꢁ1 for P]O … H2OeEu. The same reversal in
the sign of the temperature dependence is also found for Yb and
seems to be indicative of the differing nature of the interaction. It is
The reaction between scandium and lanthanide triflates

A.W.G. Platt, K. Singh / Journal of Molecular Structure 1111 (2016) 180e184
183
Table 3
Structural parameters for Mes3P-X.
Mes3P
Mes3PO
[Mes3PO]3H3Oþ
PeC
1.837(3)
4.76(12)
2.72(5)
1.828(3)
4.97(3)
1.821(14)
4.96(14)
Me(a) … Me(a)
C(a) … P
C(a) … O
CePeC
Fig. 3. The Structure of [Mes3PH]Cl$HCl$2H2O Chloride ions, water, HCl and carbon
and hydrogen atoms omitted for clarity.
2.89(1)
110.2(1.1)
2.89(3)
111.5(2.3)
105.9(3.7)
distance ranges from 1.801 to 1.896 Å with an average of 1.833 Å.
The CePeC bond angles vary considerably in the previously re-
ported structures from 106 to 118ꢀ (average 112.4ꢀ) and the average
of 114.8ꢀ found here lies within that range. There are no in-
teractions between the PeH and H2O, HCl and Clꢁ but hydrogen
bonding is found between the lattice water, HCl and chloride ions.
Details are given as supplementary information in Table S1. In the
absence of short contacts with the phosphonium hydrogen the PeH
distance of 1.311 Å lies within the range of 1.341e1.263 Å (average
1.301 Å) reported for the Mes3PHþ ion reported in other com-
pounds [23e26].
Table 4
31P NMR data for lanthanide triflate/Mes3PO in CD3CN.
d
/ppm
W1/2/Hza
Temperature dependenceb/ppmKꢁ1
Ln
Nd
Eu
Ho
Er
Yb
Lu
Mes3PO
31.9
29.9
38.4
28.8
29.1
32.3
26.9
71
135
63
220
13
0.04
ꢁ0.14
ꢁ0.15
ꢁ0.17
ꢁ0.04
ꢁ0.001
0.003
10
5
a
At 30 ꢀC.
Temperature range 30e70 ꢀC.
b
3. Conclusion
Strong complexes between Mes3PO and lanthanide ions do not
form due to a combination of steric factors related to the congestion
around the donor atom and probably the strong solvation of the
lanthanide starting materials. The interaction which leads to
increased solubility of Mes3PO observed in reactions with the
lanthanide ions is probably due to hydrogen bonding with coor-
dinated water molecules in Ln(NO3)36H2O and Ln(CF3SO3)36H2O
used in the reactions. Trimesitylphosphine itself reacts with hy-
drated lanthanide ions to form the well-defined phosphonium salt
rather than forming hydrogen bonded complexes.
(Ln ¼ Eu, Lu) and lanthanide nitrates (Ln ¼ La, Ce, Eu, Yb and Lu)
and Mes3P in CD3CN was carried out to examine the possible for-
mation of hydrogen bonded phosphine complexes. If such an
interaction were to occur a larger paramagnetic shift might be
expected than is observed for hydrogen bonded R3PO as the effect
would be transmitted through 3 bonds rather than 4. The NMR
spectra show in addition to a signal from unreacted phosphine
at ꢁ36.5 a peak at ꢁ26.9 ppm 1JPH 510 Hz which was independent
of the metal ion used. This has very similar shift and coupling
constant to that reported for Mes3PHþ [22]. The formation of the
phosphonium salt undoubtedly proceeds via the protonation of the
phosphine by the acidic hydrogens of the coordinated water mol-
ecules as indicated in Eq. (1).
4. Experimental
Data for x-ray structures were collected on a Bruker APEX 2000
CCD diffractometer using graphite-monochromated Mo-Ka radia-
LnX3ðH2OÞn þ Mes3P/LnX2ðOHÞðH2OÞnꢁ1 þ Mes3PHþXꢁ
tion,
l
¼ 0.71073 Å.
The data were corrected for Lorentz and polarisation effects and
empirical absorption corrections applied. Structure solution by
direct methods and structure refinement based on full-matrix
least-squares on F2 employed SHELXTL version 6.10 [27].
Hydrogen atoms were included in calculated positions
(CeH ¼ 0.95e0.98 Å) riding on the bonded atom with isotropic
displacement parameters set to 1.5 Ueq(C) for methyl H atoms and
1.2 Ueq(C) for all other H atoms. All non-H atoms were refined with
anisotropic displacement parameters.
(1)
This was confirmed by carrying out the reaction with ScTf(D2O)6
which produced a characteristic 1:1:1 triplet (1JPD ¼ 76 Hz) ex-
pected from PeD coupling. Further confirmation was obtained by
preparing a fully characterised Mes3PHþ salt by reaction of Mes3P
with aqueous HCl in CH3CN. Single crystals of Mes3PHþ
Clꢁ.HCl$2H2O formed spontaneously from the reaction mixture.
The 31-P NMR spectrum showed the expected single signal
at ꢁ25.6 1JPH ¼ 511 Hz. Hydrogen bonding of the phosphine to the
coordinated water is probably the first step in this reaction.
The structure of Mes3PHþClꢁ.HCl$2H2O is shown in Fig. 3, de-
tails of the data collection and refinement in Table 5 and selected
bond distances and angles in Table 6. The structure is similar to
those reported for the Mes3PHþ with other anions [23e26]. The
PeC distances, at an average of 1.799 Å, are slightly below the lower
end of the range reported for other structures where the PeC
Infrared spectra were recorded with a resolution of 2 cmꢁ1 on
a Thermo Nicolet Avatar 370 FT-IR spectrometer operating in ATR
mode. Samples were compressed onto the optical window and
spectra recorded without further sample pre-treatment.
NMR spectra were obtained on a JEOL ECX e400
Trimesitlyphosphine oxide Trimesitylphosphine (5.08
g
13 mmol) was suspended in 25 mL acetone and 2.59 g 30% aqueous
hydrogen peroxide was added over 10 min. The suspension was

184
A.W.G. Platt, K. Singh / Journal of Molecular Structure 1111 (2016) 180e184
Table 5
Crystal data and structure refinement for Mes3PHþ.Clꢁ.HCl$2H2O.
Empirical formula
Formula weight
Temperature
C27 H39 Cl2 O2 P
497.45
150(2) K
Wavelength
0.71073 Å
Crystal system
Space group
Unit cell dimensions
Orthorhombic
P2(1)2(1)2(1)
a ¼ 11.6750(19) Å
b ¼ 14.603(2) Å
c ¼ 15.704(2) Å
2677.4(7) Å3
a
b
g
¼ 90ꢀ
¼ 90ꢀ
¼ 90ꢀ
Volume
Z
4
Density (calculated)
Absorption coefficient
F(000)
Crystal size
Theta range for data collection
Index ranges
Reflections collected
Independent reflections
Completeness to theta ¼ 26.00ꢀ
Absorption correction
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2sigma(I)]
R indices (all data)
1.234 Mg/m3
0.324 mmꢁ1
1064
0.16 ꢂ 0.09 ꢂ 0.04 mm3
1.90e26.00ꢀ
ꢁ14 ꢃ h ꢃ 14, ꢁ18 ꢃ k ꢃ 17, ꢁ19 ꢃ l ꢃ 19
21,143
5255 [R(int) ¼ 0.1783]
100.0%
Empirical
0.862 and 0.488
Full-matrix least-squares on F2
5255/4/298
0.748
R1 ¼ 0.0622, wR2 ¼ 0.0854
R1 ¼ 0.1223, wR2 ¼ 0.0980
0.01(9)
Absolute structure parameter
Largest diff. peak and hole
0.337 and ꢁ0.330 e.Åꢁ3
Table 6
html, or from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ UK: fax (þ44þ1223-336-033) or e-
mail: deposit@ccdc.cam.ac.uk.
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.molstruc.2016.01.073.
Bond lengths [Å] and angles [ꢀ] for (3).
P(1)eC(10)
P(1)eC(1)
P(1)eC(19)
P(1)eH(1)
C(10)eP(1)eC(1)
C(10)eP(1)eC(19)
C(1)eP(1)eC(19)
C(10)eP(1)eH(1)
C(1)eP(1)eH(1)
C(19)eP(1)eH(1)
1.785(4)
1.806(5)
1.810(5)
1.3117
117.4(2)
113.8(2)
113.4(2)
101.7
References
[1] D.A. Atwood (Ed.), The Rare Earth Elements: Fundamentals and Applications,
John Wiley &sons Ltd, 2012.
[2] X. Sun, H. Luo, S. Dai, Chem. Rev. 112 (2012) 2100.
[3] X.-M. Gan, R.T. Paine, E.N. Duesler, H. Noth, J. Chem. Soc. Dalton Trans. (2003)
153.
105.0
103.3
[4] J.R. Klaehn, D.R. Peterman, M.K. Harrup, R.D. Tillotson, T.A. Luther, J.D. Law,
L.M. Daniels, Inorg. Chim. Acta 361 (2008) 2522.
[5] J.H. Matonic, M.P. Neu, A.E. Enriquez, R.T. Paine, B.C. Scott, J. Chem. Soc. Dalton
Trans. (2002) 2328.
[6] A. Bowden, K. Singh, A.W.G. Platt, Polyhedron 42 (2012) 30.
[7] A. Bowden, P.N. Horton, A.W.G. Platt, Inorg. Chem. 50 (2011) 2553.
[8] A. Bowden, S.J. Coles, M.B. Pitak, A.W.G. Platt, Inorg. Chem. 51 (2012) 4379.
[9] C.A. Tolman, Chem. Rev. 77 (1977) 345.
heated to 50 ꢀC for 10 min and stirred at room temperature for 2 d.
The mixture was filtered, washed with methanol and dried at the
pump to give 5.06 g white solid. Recrystallisation from acetonitrile
gave crystals of [Mes3PO]2CH3CN suitable for x-ray diffraction.
Synthesis Mes3PHþCl¡.HCl·2H2O
Trimesitylphosphine 0.50 g (1.25 mmol) was suspended in
CH3CN (4.0 g) and 0.22 g 36% aqueous HCl, (2.17 mmol) was added.
The mixture cleared on addition and crystals were deposited on
standing overnight. The yellow crystals were filtered, washed with
CH3CN and dried at the pump to give 0.39 g (63%)
[10] A.P. Hunter, A.M.J. Lees, A.W.G. Platt, Polyhedron 26 (2007) 4865.
[11] A.M.J. Lees, A.W.G. Platt, Polyhedron 67 (2014) 368.
[12] A. Bowden, A.M.J. Lees, A.W.G. Platt, Polyhedron 91 (2015) 110.
[13] Q. Li, H. Zhu, H. Zhu, X. Yang, W. Li, J. Cheng, Spectrochim. Acta 132 (2014)
271.
[14] A. Zabardasti, A. Kakanejadifard, H. Goudarziafshar, M. Salehnassaj,
Z. Zohrehband, F. Jaberansari, M. Solimannejad, Comp. Theor. Chem. 1014
(2013) 1.
[15] S.X. Tian, X.X. Chi, K.Z. Xu, Chem. Phys. 276 (2002) 263.
[16] A.C. Legon, L.C. Willoughby, Chem. Phys. 74 (1983) 127.
[17] E.C. Alyea, S.A. Dias, G. Ferguson, M. Parvez, Inorg. Chim. Acta 37 (1979) 45.
[18] E.C. Alyea, S.A. Dias, S. Stevens, Inorg. Chim. Acta 44 (1980) L203.
[19] J.Malito, E.C.Alyea Inorg. Chim. Acta 144 (188) 155.
[20] A. Bayer, G.A. Bowmaker, H. Schmidtbauer, Inorg. Chem. 35 (1996) 5959.
[21] G.P. Schiemenz, Z. Naturforsch. 62b (2007) 235.
Analysis expected(found) C 65.19(65.00) H7.90(8.04)
NMR 1H (400 MHz) 1.90(s) 9H CH3, 2.33(s) 9H CH3 2.52(s) 9H
1
CH3, 6.94(s) 3H CH, 7.07(s) 3H CH, 9.4(d) JPH 510 Hz 1H PH; 31P
(161 MHz) CDCl3 d ꢁ25.6 1JPH 510 Hz.
ScTF36D2O was prepared by recrystallising the hydrated salt
once from D2O.
[22] E.C. Alyea, J. Malito, Phosphorus Sulfur Silicon 46 (1989) 175.
[23] G. Menard, L. Tran, D.W. Stephan, J. Chem. Soc. Dalton Trans. 42 (2013) 13685.
[24] T. Xu, E.Y.-X. Chen, J. Am. Chem. Soc. 136 (2014) 1774.
[25] G. Menardr, D.W. Stephan, J. Am. Chem. Soc. 132 (2010) 1796.
[26] C. Jiang, O. Blacque, H. Berke, Organometallics 28 (2009) 5233.
[27] G.M. Sheldrick, SHELXTL Version 6.10, Bruker AXS, Inc., Madison, Wisconsin,
USA, 2000.
Appendix A. Supplementary data
CCDC 1419070e1419072 contain the supplementary crystallo-
graphic data for (1)e(3) respectively. These data can be obtained
free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.