Optimised synthesis and characterisation of 1-adamantyltrimethylphosphonium iodide

Article abstract of DOI:10.1016/j.poly.2017.05.050

A synthetic route to multigram quantities of 1-adamantyltrimethylphosphonium iodide is reported. The synthesis starts from the commercially available precursor 1-adamantyl bromide and was optimised with respect to yield and ease of purification. The title compound is of interest to zeolite chemists as a potent organic structure-directing agent. Full spectroscopic characterisation data of all isolated intermediates and single crystal X-ray diffraction data of AdP(O)Cl₂, [AdPMe₂H]I and [AdPMe₃]I (Ad?=?1-adamantyl) are reported.

Full text of DOI:10.1016/j.poly.2017.05.050

Accepted Manuscript
Optimised Synthesis and Characterisation of 1-Adamantyltrimethylphosphoni-
um Iodide
Riad Mansour, Phillip S. Nejman, Laurence J. Taylor, Brian A. Chalmers,
Fernando Rey, Abdelkader Bengueddach, J. Derek Woollins, Alexandra M. Z.
Slawin, Petr Kilian
PII:
S0277-5387(17)30406-0
DOI:
http://dx.doi.org/10.1016/j.poly.2017.05.050
POLY 12669
Reference:
To appear in:
Polyhedron
Received Date:
Revised Date:
Accepted Date:
18 April 2017
23 May 2017
24 May 2017
Please cite this article as: R. Mansour, P.S. Nejman, L.J. Taylor, B.A. Chalmers, F. Rey, A. Bengueddach, J. Derek
Woollins, A. M. Z. Slawin, P. Kilian, Optimised Synthesis and Characterisation of 1-
Adamantyltrimethylphosphonium Iodide, Polyhedron (2017), doi: http://dx.doi.org/10.1016/j.poly.2017.05.050
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Optimised Synthesis and Characterisation of 1-
Adamantyltrimethylphosphonium Iodide
a,b
Riad Mansour, Phillip S. Nejman, Laurence J. Taylor, Brian A. Chalmers, Fernando Rey,
a
Abdelkader Bengueddach, J. Derek Woollins, Alexandra M. Z. Slawin, Petr Kilian *
c
c
c
d
c
c
c
a) Laboratoire de Chimie des Matériaux, Département de Chimie, Faculté des Sciences, Université d’Oran
Ahmed Benbella, P.O. Box 1524 El-Menouer, 31000-Oran, Algeria
1
b) Centre Universitaire Salhi Ahme Naama, P.O. Box 66, 45000-Naama, Algeria
c) EaStChem School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, United Kingdom
d) Instituto de Technologia Quimica (CSIP-UPV), Avenida de los Naranjos s/n 46022, Valencia, Spain
Keywords: Organophosphorus, Phosphonium, Synthesis, Adamantyl group, Organic
Structure-directing Agent
Abstract
A synthetic route to multigram quantities of 1-adamantyltrimethylphosphonium iodide is
reported. The synthesis starts from the commercially available precursor 1-adamantyl
bromide and was optimised with respect to yield and ease of purification. The title
compound is of interest to zeolite chemists as a potent organic structure-directing agent.
Full spectroscopic characterisation data of all isolated intermediates and single crystal X-ray
2 2 3
diffraction data of AdP(O)Cl , [AdPMe H]I and [AdPMe ]I (Ad = 1-adamantyl) are reported.
Introduction
The adamantyl group occupies a rather special position amongst alkyl groups
because of its cage structure, which confers 3D bulk, rigidity, and chemical inertness. These
attributes led to adamantyl groups being exploited in the stabilisation of highly reactive
species, such as the first isolable carbene.[1] In zeolite chemistry, an adamantyl group-
containing tetraalkylammonium hydroxide, N,N,N-trimethyl-1-adamantylammonium
hydroxide, TMAdOH (Ad = 1-adamantyl), has been used as an organic structure-directing
agent (OSDA). Several zeolite types have been synthesised using TMAdOH as an OSDA,
namely SSZ-13 (CHA), SSZ-23 (STT), and SSZ-24 (AFI).[2] The small-pore chabazite zeolite
type SSZ-13 is the most significant of these, since it has proved to be a superior acid catalyst
for the conversion of methanol to olefins,[3, 4] and a potential catalyst for reducing nitrogen
x
oxide (NO ) emissions.[5]
In contrast to tetraalkylammoniums,[6, 7] the use of structurally related
tetralkylphosphonium (TAP+) compounds as OSDAs is much less established in zeolite
chemistry. Tetraalkylphosphoniums have been used as both OSDAs and modifying agents, in
an effort to obtain more efficient P-modified zeolite catalysts and novel zeolite structures.
Examples include zeolites ITQ-26 (IWS),[8] ITQ-27 (IWW),[9, 10] ITQ-34 (ITR),[11] ITQ-49
(IRN)[12] and ITQ-53.[13] Recently, tetraalkylphosphoniums have been used in the so-called

dual-template method for the synthesis of a P-modified chabazite zeolite. Here, N,N,N-
trimethyl-1-adamantylammonium and tetraethylphosphonium cations were employed
together in order to improve the thermal stability of chabazite zeolite catalysts.[14]
However, there are no reports of adamantyl group-containing phosphorus
compounds as OSDAs in the literature. This is surprising, given the important role of its
ammonium analogue TMAdOH in chabazite synthesis. We believe this is because the
synthesis of adamantylphosphoniums remains challenging, especially compared to their
nitrogen congeners. The factors contributing to this are limited availability of potential
precursors, such as adamantylphosphine and adamantyldihalophosphines, neither of which
are commercially available. Moreover, the high reactivity of these intermediates towards
air/moisture requires the use of rigorous inert atmosphere techniques during synthetic
manipulations, adding an additional level of complexity.
The hydroxide [AdPMe
procedure from [AdPMe ]I.[15] Here we report an optimised synthetic sequence to 1-
adamantyltrimethylphosphonium iodide [AdPMe ]I, starting from commercially available 1-
3
]OH is accessible via a standard anion-exchange resin
3
3
bromoadamantane. The sequence has been designed to cater for the needs of zeolite
chemists; it is readily scalable to multigram scales, involves the minimum number of
synthetic steps, and minimises (as far as possible) the requirement for strict inert
atmosphere conditions. To facilitate monitoring of the reaction sequence progress by non-
specialists, we provide full spectroscopic characterisation data of all the isolated
intermediates. Single crystal X-ray diffraction data are also reported for completeness.
Results and Discussion
Syntheses
3
The synthetic pathway to [AdPMe ]I reported in this work is shown in Scheme 1. The
pathway consists of four steps with three isolated intermediates.
In the first step, Friedel-Crafts-like conditions were used to phosphorylate 1-
bromoadamantane. This was followed by aqueous workup to yield crude AdP(O)Cl
crude product was purified by column chromatography on silica, to give pure AdP(O)Cl
an air stable colourless powder in 68% yield. Whilst the literature procedures use AlBr ,[16,
7] we have used the more readily available AlCl to obtain comparable yields. The purity of
2
. The
2
as
3
1
3
3
1
1
1
the product was established chiefly by P{ H} and H NMR spectroscopy. For completeness,
1
3
1
we also provide C{ H} NMR and IR spectroscopic data. Our data are in full agreement with
those reported earlier.[17, 18]
The reduction of AdP(O)Cl
procedure,[16] and afforded AdPH
purification of the oily product was needed providing pure starting material (AdP(O)Cl
used in the reaction. This is the preferred approach since AdPH is air sensitive; its
purification is hence rather more demanding (distillation under inert atmosphere) compared
to the purification of the air stable AdP(O)Cl precursor. The purity of AdPH was assessed
2
with LiAlH
as colourless oil in a quantitative yield. No further
) was
4
was performed as per the literature
2
2
2
2
2

3
1
1
1
13
1
by P{ H} and H NMR spectroscopy, for completeness we also provide the C{ H} NMR
data. Spectroscopic data are in full agreement with those reported earlier.[17] It should be
noted that an alternative route to AdPH
reported by Imamoto.[19] However, this route proved less efficient in our hands, with the
above synthesis via AdP(O)Cl proving significantly more reliable.
In the third step, AdPH was treated with excess MeI using methanol as the solvent.
The reaction affords the hydroiodide [AdPMe H]I as the sole phosphorus containing product
in a near quantitative yield. The exhaustive alkylation to the phosphonium iodide (according
to the equation AdPH + 3 MeI →[AdPMe ]I + 2 HI) did not proceed, even when a large
2
via the use of Grignard chemistry has been
2
2
2
2
3
excess of MeI was used coupled with both extended reaction times and heating. This is in
agreement with the early work by Hays, who observed that the hydroiodides of trialkyl
phosphines are exceptionally resistant to further alkylation due to being the adduct of a
strong acid (HI) and a highly basic phosphine (PR
has been reported in the literature, the experimental details and characterisation data are
somewhat limited.[21] Moreover, the literature procedure suggests isolation of AdPMe as
an intermediate. This is obtained by in situ neutralisation of the initially formed hydroiodide
3 2
).[20] Whilst alkylation of AdPH with MeI
2
[
AdPMe
2
H]I with NaOH. We have found it more convenient to isolate the hydroiodide
H]I, which is obtained as crystalline material and easily purified by washing with a
[AdPMe
2
non-polar solvent, such as hexane. The hydroiodide [AdPMe
2
H]I was fully characterised
using H, P and C NMR spectroscopy, HRMS, IR spectroscopy and elemental analysis.
Neutralisation of [AdPMe H]I with NaOH and subsequent treatment of the formed
AdPMe with MeI afforded [AdPMe ]I as a white solid in a very good yield (88%). Analytically
pure material was obtained with minimal purification (washing with hexane), and was fully
1
31
13
2
2
3
1
31
13
characterised using H, P and C NMR spectroscopy, HRMS, IR spectroscopy and
elemental analysis. Our characterisation data is broadly in agreement with that reported
earlier, which were obtained on [AdPMe
3
]I synthesised via a different route.[22]
1
. PCl /AlCl
3
3
2. H O
LiAlH4
quant.
2
O
Br
P
PH2
68%
Cl
Cl
AdPH2
AdP(O)Cl2
MeI
H
97%
I
1. NaOH
I
2. MeI
P
88%
P
[AdPMe3]I
[AdPMe H]I
2
Scheme 1 Synthetic pathway to [AdPMe
3
]I reported in this paper.

Crystallography
Crystal structures of AdP(O)Cl
2
, [AdPMe
2
3
H]I and [AdPMe ]I are shown in Figure 1, with
selected data in Table 1 and Table 2. The AdP(O)Cl
2
is molecular, whilst the other two
structures have ionic separated phosphonium cations and iodide anions. In each case the
phosphorus atom adopts a slightly distorted tetrahedral geometry, indicating that
attachment of the bulky adamantane group does not introduce substantial angular strain
into the phosphorus environment. The P1-C1 bonds are crystallographically identical in all
three structures and as expected for a normal P-C single bond.
2 2 3
Figure 1 Left to right: The crystal structures of AdP(O)Cl , [AdPMe H]I and [AdPMe ]I. Carbon-bound hydrogen
atoms are omitted for clarity. Ellipsoids are plotted at the 40% level.
2 2 3
Table 1 Selected bond lengths (Å) and angles (°) for AdP(O)Cl , [AdPMe H]I and [AdPMe ]I.
AdP(O)Cl
P1-C1
2
1.816(3)
1.455(2)
P1-Cl1
P1-Cl2
2.0250(12)
2.0259(10)
P1=O
C1-P1-Cl1
C1-P1-O1
106.38(9)
Cl1-P1-Cl2
O1-P1-Cl1
101.32(5)
116.69(12)
112.57(10)
[
AdPMe
2
H]I
P1-C1
1.8246(17)
111.34(8)
P1-C11
P1-C12
1.7843(19)
1.7759(19)
C1-P1-C11
C1-P1-C12
112.67(9)
C11-P1-C12
109.39(10)
[
3
AdPMe ]I
P1-C1
1.817(11)
1.786(14)
P1-C12
P1-C13
1.778(14)
1.789(12)
P1-C11
C1-P1-C11
C1-P1-C12
109.7(6)
111.1(6)
C1-P1-C13
111.9(5)
110.5(8)
C11-P1-C12

Conclusion
An optimised synthetic sequence for multigram quantities of an adamantyl group containing
3
phosphorus based OSDA [AdPMe ]I is reported. The synthesis has been extensively tested
and optimised for reproducibility. Particular attention has been paid to limiting the need for
specialist procedures, and minimising laborious purification steps. Included in the sequence
is column chromatography on (air stable) AdP(O)Cl
2
. No purification was needed in the
following two steps (producing AdPH and [AdPMe
2
2
H]I), providing the inert atmosphere
conditions were maintained throughout the reaction and work-up. In the next step,
extraction using an aqueous/organic biphasic system was required to remove salts from the
2
in situ formation of AdPMe . This extraction was performed under an inert atmosphere
using the cannulation technique, and is likely to be the most demanding purification
procedure. Single crystal X-ray data revealed uncongested phosphorus centres in the three
3
crystalline materials obtained, including the title compound, [AdPMe ]I.
Experimental
General
Unless otherwise stated, all manipulations were performed under an oxygen-free nitrogen
atmosphere using standard Schlenk techniques or under argon atmosphere using Saffron
glove box. 1-Bromoadamantane was obtained from Sigma-Aldrich. Solvents were collected
from an MBraun Solvent Purification System or dried and stored according to common
procedures.[23] IR spectra were collected on a Perkin Elmer 2000 NIR/Raman Fourier
1
13
31
Transform spectrometer. H, C and P NMR spectra were obtained on either a Bruker
Avance II 400, Bruker Avance III 500 or Jeol GSX Delta 270 spectrometer with δ and δ
relative to TMS, residual solvent peaks (CDCl ; δ 7.26, δ 77.2 ppm) were used for
calibration. 85% H PO was used as an external standard for P NMR. All measurements
H
C
3
H
C
3
1
3
4
were performed at 25 °C with shifts reported in ppm. Mass spectra were acquired by the
EPSRC UK National Mass Spectrometry Facility at Swansea University using nanospray
ionisation (NSI). Elemental analyses were performed by Stephen Boyer at the London
Metropolitan University.
AdP(O)Cl
An adapted literature procedure was used.[16, 17] AlCl
bromoadamantane (21.73 g, 0.10 mol) were cooled in an ice bath and PCl
was added portionwise over 30 mins. Upon complete addition the reaction was heated to
0 °C for 24 h. The excess PCl was removed in vacuo and the solid washed with hexane (200
mL). The remaining procedure was performed in air as the compounds are air stable. The
solid was added to CH Cl (500 mL) and the resulting suspension was cooled in an ice bath.
2
3
(20.20 g, 0.15 mol) and 1-
(150 mL, 2.0 mol)
3
9
3
2
2
Water (250 mL) was added dropwise until the vigorous reaction subsided. The organic layer
was isolated and dried over magnesium sulfate. Removal of the solvent in vacuo afforded
the crude product as a pale brown solid. Purification was performed by flash column
2 2
chromatography (silica/CH Cl ). The product was obtained as a white powder (17.18 g,

0
.067 mol, 68%). Crystals suitable for single crystal X-ray diffraction were obtained by slow
1
3
1
31
1
evaporation of a solution in CH
that previously reported.[18]
2 2
Cl . C{ H} and P{ H} data was in good agreement with
1
3
3
H NMR (500 MHz, CDCl
H, CH ), 1.84 – 1.74 (br m, 6 H, CH
H{ P} NMR (500 MHz, CDCl ): δ 2.18 (br s, 3 H, CH), 2.09 (br s, 6 H, CH
H, CH ).
q 2
C NMR (125 MHz, CDCl ): δ 48.5 (d, JCP = 88.2 Hz, C ), 35.8 (d, JCP = 2.7 Hz, CH ), 34.9 (d,
3
): δ 2.21 – 2.15 (br m, 3 H, CH), 2.09 (dd, JHP = 8.0 Hz, JHH = 2.7 Hz,
6
1
2
2
).
31
3
2
), 1.84 – 1.74 (br m,
6
2
1
2
3
3
3
1
4
3
3
J
1
CP = 4.2 Hz, CH
2
), 27.5 (d, JCP = 15.5 Hz, CH).
P NMR (202 MHz, CDCl ): δ 65.2 (br m (≈s)).
P{ H} NMR (109 MHz, CDCl ): δ 65.2 (s).
3
1
1
3
-
1
IR (KBr): νmax/cm 2924s (νC-H), 2857s (νC-H), 1453m, 1264s (νP=O), 542s.
AdPH
An adapted literature procedure was used.[16] To a cooled suspension (0 °C) of LiAlH
g, 0.13 mol) in diethyl ether (150 mL) was added dropwise a solution of AdP(O)Cl (17.00 g,
.067 mol) in diethyl ether (120 mL). Upon complete addition, the reaction was heated to
2
4
(5.00
2
0
reflux for 1 h. The reaction was cooled in an ice bath and degassed water (100 mL) was
added cautiously (vigorous reaction!). The organic layer was removed and the aqueous layer
extracted with diethyl ether (2 x 50 mL), the combined organic fractions were dried over
magnesium sulfate. Removal of the solvent afforded the product as a colourless oil (11.12 g,
1
3
1
31
1
0
.066 mol, 99%). C{ H} and P{ H} data was in good agreement with that previously
reported.[17]
1
1
H NMR (500 MHz, CDCl
3
): δ 2.66 (d, JHP = 192.7 Hz, 2 H, PH
).
): δ 3.06 – 2.34 (m, 2 H, PH
), 1.73 – 1.63 (m, 6 H, CH ).
2
), 1.93 (br s, 3 H, CH), 1.80 –
1
.77 (m, 6 H, CH
2
), 1.73 – 1.63 (m, 6 H, CH
H{ P} NMR (500 MHz, CDCl
.7 Hz, 6 H, CH
2
1
31
3
3
2
), 1.93 (s, 3 H, CH), 1.79 (d, JHH
=
2
2
2
1
3
2
3
C NMR (125 MHz, CDCl
3
): δ 44.7 (d, JCP = 8.2 Hz, CH
2
), 36.3 (s, CH
2
), 28.9 (d, JCP = 7.7 Hz,
CH).
3
3
1
1
1
P NMR (202 MHz, CDCl
3
): δ −82.3 (t, JPH = 192.7 Hz).
1
3
P{ H} NMR (109 MHz, CDCl ): δ −82.3 (s).
+
−
[
2
AdPMe H] I
To a MeOH (40 mL) solution of AdPH
2
(6.13 g, 0.036 mol) was added methyl iodide (20.44 g,
0
.14 mol). The reaction was heated to 30°C under reflux conditions for 17 h. The remaining
procedure was carried out in air, as the compounds are air stable. The volatiles were
removed in vacuo and the resulting solid was washed with hexane (50 mL). Drying in vacuo
afforded the product as a white solid (11.32 g, 0.035 mol, 97%). Crystals suitable for single
crystal X-ray diffraction were obtained by diffusion of diethyl ether into a CH
the product.
2 2
Cl solution of

−1
Anal. calcd. for C12H22IP (324.19 g mol ): C, 44.46; H, 6.84. Found: C, 44.37; H, 6.83.
1
1
3
3
H NMR (500 MHz, CDCl ): δ 7.16 (d of septets, JHP = 489.0 Hz, JHH = 5.4 Hz, 1 H, P-H), 2.16
2
3
3
3 2
(br s, 3 H, CH), 2.06 (dd, JHP = 14.1 Hz, JHH = 5.4 Hz, 6 H, P(CH ) H), 1.97 (dd, JHP = 6.7 Hz,
3
1
3
1
3
3
3
J
HH = 2.4 Hz, 6 H, CH
2
), 1.85 – 1.75 (m, 6 H, CH
3
2
).
31
H{ P} NMR (500 MHz, CDCl
3
): δ 7.16 (h, JHH = 5.4 Hz, 1 H, P-H), 2.16 (br s, 3 H, CH), 2.06 (d,
3
J
3
HH = 5.4 Hz, 6 H, P(CH
3
)
2
H), 1.97 (d, JHH = 2.4 Hz, 6 H, CH
C NMR (125 MHz, CDCl ): δ 36.1 (s, CH ), 35.6 (s, CH ), 29.9 (d, JCP = 47.8 Hz, C
CP = 10.6 Hz, CH), 1.3 (d, JCP = 50.4 Hz, P(CH H).
): δ 12.5 (d, JPH = 489.0 Hz).
P{ H} NMR (109 MHz, CDCl ): δ 12.5 (s).
2 2
), 1.85 – 1.75 (m, 6 H, CH ).
1
3
2
2
q
), 26.9 (d,
1
J
1
3 2
)
1
P NMR (109 MHz, CDCl
3
1
1
3
+
+
+
+
] ((M+O-
HRMS (NSI ): m/z (%) 521.1949 (15) [C24
H
44
+
P
2
I] (M
2
-I ), 425.2733 (20) [C24
H
43
P
2
O
2
+
+
+
HI)
2
H ), 213.1399 (100) [C12
H
22PO] (M+O-I ), 197.1453 (50) [C12
H
22P] (M-I).
-
1
IR (KBr): νmax/cm 2957m (νC-H), 2913s (νC-H), 2849m (νC-H), 1298m, 973br s.
+
−
[
AdPMe
To a suspension of [AdPMe
aqueous solution of NaOH (6.50 g in 100 mL H
3
] I
+
−
2
H] I (5.00 g, 0.015 mol) in hexane (50 mL) was added an
O, 0.16 mol). The mixture was stirred
2
vigorously for 15 mins, then the organic layer was removed and the aqueous layer extracted
with hexane (2 x 50 mL). The combined organic fractions were dried over magnesium
sulfate, filtered and the solvent removed in vacuo. MeOH (70 mL) was added, followed by
methyl iodide (4.26 g, 0.030 mol) and the reaction mixture was stirred at room temperature
for 5 h. The remaining procedure was carried out in air, as the compounds are air stable.
The volatiles were removed in vacuo and the crude solid was washed with hexane (50 mL).
Drying in vacuo gave product as a white solid (4.46 g, 0.013 mol, 88%). Crystals suitable for
single crystal X-ray diffraction were obtained by diffusion of ether into a solution of the
product in CH
2 2
Cl .
−
1
Anal. calcd. for C12
H
22IP (338.20 g mol ): C, 46.16; H, 7.15. Found: C, 46.27; H, 7.08.
1
3
3
H NMR (400 MHz, CDCl
H, CH ), 1.84 – 1.80 (br m, 6 H, CH
H{ P} NMR (400 MHz, CDCl ): δ 2.15 – 2.09 (br m, 3 H, CH), 1.88 (d, JHH = 3.2 Hz, 6 H, CH
.84 – 1.80 (br m, 6 H, CH ), 1.76 (d, JHH = 0.9 Hz, 9 H, P(CH
3
): δ 2.15 – 2.09 (br m, 3 H, CH), 1.88 (dd, JHP = 6.0 Hz, JHH = 3.2 Hz,
2
6
1
2
2 3 3
), 1.76 (d, JHP = 13.5 Hz, 9 H, P(CH ) ).
31
3
3
2
),
5
1
2
3 3
) ).
1
3
3
3
3
4
2
C NMR (100 MHz, CDCl
3
): δ 35.2 (d, JCP = 1.1 Hz, CH
2
), 33.6 (d, JCP = 1.3 Hz, CH
2
), 27.0 (d,
1
J
3 3
CP = 10.3 Hz, CH), 3.3 (d, JCP = 53.0 Hz, P(CH ) ).
1
P NMR (109 MHz, CDCl
3
): δ 33.7 (br s).
1
1
P{ H} NMR (109 MHz, CDCl ): δ 33.7 (s).
3
+
+
+
+
HRMS (NSI ): m/z (%) 549.2246 (20) [C26
H
48
P
2
I] (M
2
-I ), 331.2543 (10) [C22
H
36P]
+
+
2 2
(Ad PMe ), 211.1602 (100) [C13H24P] (M-I).
-
1
IR (KBr): νmax/cm 2953m (νC-H), 2907s (νC-H), 2852m (νC-H), 1453m, 982s, 971s.
X-ray Diffraction.

CCDC 1544650-1544652 contains the supplementary crystallographic data for this paper.
These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
Data for AdP(O)Cl
graphite monochromator) at a temperature of −100°C to a maximum 2θ value of 50.6°. Data
for [AdPMe ]I were collected on a Rigaku XtaLAB P200 diffractometer using multi-layer
mirror monochromated Mo-Kα radiation at a temperature of −180 ± 1°C to a maximum 2θ
value of 50.6°. Multiple data collections were conducted for [AdPMe ]I, with crystals grown
2 2
and [AdPMe H]I were collected using a Rigaku SCX-Mini (Mo–Kα,
3
3
from a variety of solvents. The best quality data set was used for refinements. Although this
crystal data set appears to be of lower quality upon first inspection, it is sufficient to
demonstrate the connectivity for the purposes of this work. The large residual electronic
density lies close to the iodine atom and may reflect some slight disorder in the position of
this high Z atom. Attempts to refine this electron density as a partial weight iodine were
unproductive. All data were corrected for Lorentz, polarisation and long-term intensity
fluctuations. Absorption effects were corrected on the basis of multiple equivalent
reflections. Hydrogen atoms were refined using the riding model in all cases. The data for all
compounds were collected and processed using CrystalClear (Rigaku).[24-26] The crystal
structures were solved using direct methods and refined by heavy–atom Patterson methods
and expanded using Fourier techniques.[27-29] All calculations were performed using the
CrystalStructure crystallographic software package except for refinement which was
performed using SHELXL–97/2013.[30-32] Table 2 lists the details of data collections and
refinements. Images of crystal structures were obtained using OLEX-2[33] with all other
manipulations carried out using Mercury 3.5.[34]
Table 2 Crystallographic data for AdP(O)Cl
2
, [AdPMe
2
H]I and [AdPMe
3
]I.
AdP(O)Cl
OP
253.09
colourless, prism
0.260 × 0.110 × 0.090
monoclinic
P 1 21/n 1
7.0406(14)
10.702(3)
15.181(4)
90
2
[AdPMe H]I
2
3
[AdPMe ]I
Formula
M
r
C
10
H15Cl
2
C
12
H22IP
C13 H24 I P
338.21
colourless, platelet
0.100 × 0.100 × 0.010
triclinic
324.18
Colour/Habit
Crystal Dimensions [mm]
Crystal System
Space Group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
colourless, prism
0.440 × 0.270 × 0.180
monoclinic
P 1 21/n 1
7.5806(5)
12.7807(8)
14.1507(9)
90
104.460(4)
90
1327.57(15)
4
P-1
6.6147(19)
7.318(2)
15.351(5)
91.933(11)
92.638(7)
90.395(9)
741.8(4)
2
97.383(10)
90
1134.4(5)
4
γ [°]
V [Å ]
3
Z
-
3
ρcalcd. [g cm ]
1.482
1.622
1.514
F
000
528.0
6.78
648.0
24.99
340.0
22.40
-
1
μ [cm ]

50.6
50.8
50.6
2θ
max
Measured refln.
Unique refln.
9432
2065
10668
2319
10326
2640
R
int
0.0756
0.0407
0.1069
1.063
0.0217
0.0169
0.0419
1.063
0.0957
0.0804
0.2563
1.190
R [I>2σ(I)]
wR (F , all data)
GOOF
2
-
3
Largest peak/hole [e Å ]
0.42/–0.32
0.36/–0.28
5.90/–1.12
Acknowledgements
This work was financially supported by the EPSRC (grant numbers EP/L505079/1 and
EP/M506631/1) and COST action SM1302 SIPs. The authors thank the University of St
Andrews NMR Service and the EPSRC UK National Mass Spectrometry Facility at Swansea
University (NMSF).
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I
CH3
CH3
Br
P
H C
3
[
AdPMe3]I
phosphorus based organic
structure-directing agent
Synopsis:
A synthetic route to multigram quantities of 1-adamantyltrimethylphosphonium iodide is
reported, together with single crystal X-ray diffraction data of AdP(O)Cl , [AdPMe H]I and
AdPMe ]I (Ad = 1-adamantyl).
2
2
[
3