Ditertiary phosphines bearing a –N–C–C(O)–N(H)– linker and their corresponding dichloroplatinum(II) complexes

Article abstract of DOI:10.1080/10426507.2018.1542397

The preparation of a small library of new –N–C–C(O)–N(H)– modified ditertiary phosphines is reported along with their square-planar dichloroplatinum(II) complexes. All compounds were characterized by ³¹P{¹H} and ¹H NMR spectroscopy, FT–IR spectroscopy and elemental analysis. The single crystal X-ray structures of four Pt^II complexes have been determined. Intra- (N–H···N) and intermolecular (N–H···N) hydrogen bonding is principally observed.

Full text of DOI:10.1080/10426507.2018.1542397

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: https://www.tandfonline.com/loi/gpss20
Ditertiary phosphines bearing a –N–C–C(O)–N(H)–
linker and their corresponding dichloroplatinum(II)
complexes
Mark R. J. Elsegood, Andrew J. Lake, Martin B. Smith & George W. Weaver
To cite this article: Mark R. J. Elsegood, Andrew J. Lake, Martin B. Smith & George W. Weaver
(
2018): Ditertiary phosphines bearing a –N–C–C(O)–N(H)– linker and their corresponding
dichloroplatinum(II) complexes, Phosphorus, Sulfur, and Silicon and the Related Elements, DOI:
0.1080/10426507.2018.1542397
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2018.1542397
Ditertiary phosphines bearing a –N–C–C(O)–N(H)– linker and their corresponding
dichloroplatinum(II) complexes
Mark R. J. Elsegood, Andrew J. Lake, Martin B. Smith, and George W. Weaver
Department of Chemistry, Loughborough University, Loughborough, Leics, UK
ABSTRACT
ARTICLE HISTORY
The preparation of a small library of new –N–C–C(O)–N(H)– modified ditertiary phosphines is reported
along with their square-planar dichloroplatinum(II) complexes. All compounds were characterized by
Received 5 September 2018
Accepted 24 September 2018
3
1
1
1
P{ H} and H NMR spectroscopy, FT–IR spectroscopy and elemental analysis. The single crystal X-ray
II
KEYWORDS
Ditertiary phosphine; amide;
platinum; X-ray
structures of four Pt complexes have been determined. Intra- (N–HꢀꢀꢀN) and intermolecular (N–HꢀꢀꢀN)
hydrogen bonding is principally observed.
crystallography; H-bonding
GRAPHICAL ABSTRACT
1
. Introduction
ditertiary aminomethylphosphines has not received much
[8]
attention, although phosphine ligands with amide groups
Functionalised phosphorus(III) ligands are widely appreciated
as excellent ligands for stabilizing metal centers in various oxi-
dation states and coordination numbers. In this regard, one
important class of ditertiary phosphines are the aminomethyl
based ligands which have been recently reviewed by B ꢀa lint
[9]
have previously been documented. We describe here a small
series of new –N–C–C(O)–N(H)– modified ditertiary phos-
phines along with some simple coordination studies towards
square planar metal centers. The X-ray structures of four
dichloroplatinum(II) examples have been determined.
[1]
et al. The versatility of such ligands can be appreciated in
Chart 1 which demonstrates the various positions where struc-
tural modification can readily be accomplished through simple
chemical manipulation. For example, monodentate aminome-
thylphosphines can be realized through appropriate choice of
amine and correct stoichiometry of trivalent phosphorus
[
2]
reagent such as R PCH OH. Ditertiary aminomethylphos-
2
2
[3]
phines can likewise be synthesized through standard methods
that enable both control of the functionality of the central amine
and R groups on both P donor atoms. By introducing further
III
modification of the alkyl/aryl group on N, it has been shown
possible to introduce a range of additional functional groups
[
4]
(
e.g. carboxylic acids ) and also enable the preparation of tetra-
[5]
phosphines. Grafting these ligands onto various dendri-
meric and carbon supports has also been demonstrated.
[6]
[7]
The inclusion of amide functionality into the N-backbone of Chart 1. Cartoon showing modification options for (aminomethyl)phosphines.
CONTACT Martin B. Smith m.b.smith@lboro.ac.uk Department of Chemistry, Loughborough University, Loughborough, Leics LE11 3TU, UK.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpss.
ß 2018 Taylor & Francis Group, LLC

2
M. R. J. ELSEGOOD ET AL.
0
Scheme 1. Synthesis of platinum(II) complexes 4a–d. (i) RNH
MeOH, (iv) PtCl (g -cod), CH Cl .
2 2 2
2
, DCC (N,N -dicyclohexylcarbodiimide), THF (ii) Pd/C, C
6
H10, absolute EtOH, (iii) 2 equiv. Ph
2
PCH
2
OH,
4
Table 1. Selected experimental and characterizing data for 1a–4d.
1
a,b
f
–1 l, m
H (ppm)
Microanalysis (%)
H
IR (cm )
31
1
a
n
Yield (%)
NH
PCH
2
P{ H} (ppm)
C
N
ꢀ
NH
ꢀ
CO
m/z
b
b
þ
1
1
1
1
2
2
2
2
3
3
3
3
4
4
4
4
a
a
b
c
d
a
b
c
d
a
b
c
d
a
b
c
67
92
60
76
98
91
88
93
64
99
75
77
97
99
95
87
9.96, 7.55
9.99
67.16 (67.59) 5.67 (5.67)
71.12 (70.89) 5.49 (5.50)
73.02 (73.39) 5.73 (5.89)
9.41 (9.85)g
8.54 (8.27)
7.85 (7.44)
3341, 1536
3252,1544
3338, 1541
1673
1656
1675
1678
1655
1696
1668
1658
1677
1684
1687
1677
1684
1684
1675
1677
284 [M]
334 [M]
372 [M]
401 [M]
150 [M]
200 [M]
238 [M]
267 [M]
b,c
þ
þ
þ
þ
þ
þ
þ
h
10.09, 7.61b
i
i
9.98, 7.45
70.23 (70.62) 5.89 (5.47) 10.24 (10.03)
3317, 1561
3341, 3322, 1561
3350, 3264, 1553
3395, 3255, 1531
3385, 3278, 1590
3300, 1519
73.40 (72.86) 6.11 (6.11) 11.32 (11.33)
8.13
8.69
8.17
8.24
7.64
8.00
8.74
8.24
3.67
3.74
3.62
3.72, 3.71
3.76 (2.0, 15.2)d
3.75 (2.8, 16.8)d
3.88 (1.2, 16.8)
3.73, 3.72
–26.4
–26.3
–26.3
–26.3
–6.4 (3411)e
–5.0 (3416)e
–8.0 (3406)e
–9.3 (3405)
74.76 (74.71) 5.86 (5.90)
4.90 (5.12)
4.16 (4.35)
3319, 1522
3314, 1500
3281, 1532
3301, 1525
3280, 1528
3305, 1529
3345, 1531
i
76.88 (76.50) 5.41 (5.79)
75.37 (74.99) 6.00 (5.99)
45.74 (45.36) 3.91 (3.75)
49.17 (49.43) 4.08 (3.83)
53.72 (53.60) 4.13 (4.17)
53.50 (53.23) 4.26 (4.36)
i
6.6.34 (6.25)
d
e
j
þ
þ
þ
þ
2.55 (2.99)
2.68 (2.96)
2.96 (3.05)
4.42 (4.43)
777 [M–Cl]
827 [M–Cl]
865 [M–Cl]
929 [M]
f
k
h
h
d
b
c
d 2
k
3
e 1
Recorded in CDCl
3
unless otherwise stated. Recorded in (CD
values in parentheses. Includes 0.25H
90 cm (4a); 314, 291 cm (4b); 313, 291 cm (4c); 316, 296 cm (4d). FAB–MS or EI–MS.
3
)
2
SO. Obscured by arom. H region.
J
PH and JPtH respectively (in Hz).
J
PtP (in Hz). Calculated
g
h
i
j
l
m
2
O. Includes 1H
2
O. Includes 0.5H
2
O. Includes 1.5 CH
Cl
2 2
. Includes 1 CH
2
Cl
2
. Recorded as pressed KBr discs.
ꢀ
PtCl 314,
–
1
–1
–1
–1
n
2
ꢁ
Table 2. Selected bond lengths (Å) and angles ( ) for 4aꢀ0.2(CHCl
3
2
)ꢀ0.8(C H
6
OS), 4bꢀ2(CHCl
3
), 4c and 4d.
b
4
aꢀ0.2(CHCl
3
)ꢀ0.8(C
2
H
6
OS)
4bꢀ2(CHCl
3
)
4c
4d
Pt(1)–P(1)
Pt(1)–P(2)
Pt(1)–Cl(1)
Pt(1)–Cl(2)
C–O
C(O)–N
P(1)–Pt(1)–Cl(2)
P(2)–Pt(1)–Cl(1)
P(1)–Pt(1)–Cl(1)
P(2)–Pt(1)–Cl(2)
Cl(1)–Pt(1)–Cl(2)
P(1)–Pt(1)–P(2)
2.229(4) [2.222(4), 2.229(4)]
2.228(4) [2.234(4), 2.223(4)]
2.357(4) [2.357(3), 2.345(4)]
2.354(4) [2.356(3), 2.370(4)]
2.2307(10)
2.2346(10)
2.3587(10)
2.3612(9)
1.219(5)
1.348(5)
170.95(4)
176.89(4)
90.13(4)
89.23(4)
87.68(4)
92.96(3)
b
2.239(3)
2.231(3)
2.355(3)
2.2151(12)a
2.2151(12)
2.3404(11)a
2.3404(11)
1.204(10)
1.349(11)
175.88(5)a
175.88(5)
87.51(5)a
2.357(3)
1.218(19) [1.217(15), 1.225(16)]
1.35(2) [1.364(17), 1.367(18)]
1.205(16)
1.273(17)
174.12(12)
173.34(11)
89.48(11)
86.39(12)
88.11(11)
95.64(11)
176.91(14) [172.14(14), 173.51(15)]
175.26(14) [175.65(13), 175.21(15)]
88.50(14) [87.81(13), 87.79(14)]
88.99(14) [86.99(12), 86.98(16)]
89.00(13) [88.94(12), 89.16(16)]
93.36(14) [96.04(13), 96.34(14)]
87.51(5)
a
89.00(6)a
95.88(7)
a
0
0
0
1
P(2) ¼ P(1 ) and Cl(2) ¼ Cl(1 ). Symmetry operations for equivalent atoms ¼ x, –y þ =2, z. Equivalent parameters for independent molecules in parentheses.
2
. Results and discussion
[10,11]
aminoacetamides 2a–d (88–98%)
and 3a–d (64–99%) by
PCH OH in MeOH,
The new ditertiary phosphines 3a–d were prepared (Scheme 1) Mannich condensation with 2 equiv. of Ph
2
2
in two steps starting from the commercially available aromatic followed known procedures reported by others and ourselves.
amines. The preparation of benzyl carbamates 1a–d (60–92%), Characterising data for all compounds are detailed in Table 1.

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
3
Figure 1. Molecular structure of 4b. All hydrogen atoms and two chloroform
solvent molecules of crystallisation have been omitted for clarity.
3
1
1
The P{ H} NMR spectra of 3a–d showed a phosphorus reson-
ance at –26ppm (CDCl ), as expected for this class of ditertiary
3
phosphine, and the FT–IR spectra (KBr disk) confirmed an ꢀ
NH
ꢂ1 [2]
absorption around 3300 cm .
Reaction of 3a–d with
4
Figure 2. The “scorpion-like” conformation in 4d. All hydrogen atoms, except
H(2) have been omitted for clarity.
PtCl (g -cod) (cod ¼ cycloocta-1,5-diene) in CH Cl gave, after
2
2
2
work-up, the corresponding complexes 4a–d in excellent iso-
31
1
lated yields (87– 99%). The P{ H} NMR data [d(P) –5.0 to
9.3 ppm, 1J 3405 to 3411Hz] are in good agreement with
N(2)–H(2)ꢀꢀꢀN(1) 100(11) and 111ꢁ respectively] which is
believed to cause the planar aromatic fluorene group to be angled
forward over the platinum(II) center to form a “scorpion-like”
–
PtP
2]
[
cis-chelation, and further supported by the presence of two
–1
ꢀPtCl absorption bands around 300 cm . Further characterizing
data for complexes 4a–d are detailed in Table 1.
[8]
conformation (Figure 2). No intramolecular H-bonding was
observed in 4aꢀ0.2(CHCl )ꢀ0.8(C H OS) and 4bꢀ2(CHCl ),
3
2
6
3
Colourless crystalline plates [4aꢀ0.2(CHCl )ꢀ0.8(C H OS),
3
2 6
allowing the phenyl/naphthyl groups more rotational freedom.
4
d], rods [4bꢀ2(CHCl )] and laths (4c), suitable for X-ray crys-
3
0
0
0
N–HꢀꢀꢀCl [N(4)ꢀꢀꢀCl(1 ) 3.292(12) Å; H(4)ꢀꢀꢀCl(1 ) 2.53(7) Å;
N(4)–H(4)ꢀꢀꢀCl(1 ) 151(13) , symmetry operator = –xþ 3/2,
tallography were obtained by slow vapor diffusion of Et O into
2
0
ꢁ
a CHCl3 or CHCl /(CH ) SO [4aꢀ0.2(CHCl )ꢀ0.8(C H OS)]
3
3 2
3
2 6
1
1
00
00
y– =2, –zþ =2 and N(6)ꢀꢀꢀCl(4 ) 3.179(11) Å; H(6)ꢀꢀꢀCl(4 )
.35(4) Å; N(6)–H(6)ꢀꢀꢀCl(1 ) 168(13) , symmetry operator
solution of the respective complex. The molecular structures of
0
0
ꢁ
0
2
=
4
bꢀ2(CHCl ) and 4c were determined using synchrotron radi-
3
1
1
1
xþ =2, –yþ =2, zþ =2] and N–HꢀꢀꢀOS(CH ) [N(2)ꢀꢀꢀO(4) 2.91(2)
3
2
ation whilst the others were determined using sealed-tube
MoKa radiation. Selected bond lengths and angles are given in
Table 2.
ꢁ
Å; H(2)ꢀꢀꢀO(4) 2.07(4) Å; N(2)–H(2)ꢀꢀꢀO(4) 172(18) ] intermo-
lecular H-bonding was observed in 4aꢀ0.2(CHCl ) ꢀ0.8(C H OS).
3
2 6
0
0
In 4bꢀ2(CHCl ), intermolecular N(2)–H(2)ꢀꢀꢀCl(2 ) [N(2)ꢀꢀꢀCl(1 )
3
Figure 1 shows the molecular structure of 4bꢀ2(CHCl ) as a
3
0
0
ꢁ
3
.324(4) Å; H(2)ꢀꢀꢀCl(2 ) 2.45Å; N(2)–H(2)ꢀꢀꢀCl(2 ) 171 ] H-
representative example of this series of dichloroplatinum(II)
compounds. All four complexes were found to adopt a
distorted square planar environment with respect to the
platinum(II) center [bond angles P(1)–Pt(1)–Cl(2) and
bonding gives rise to 1D chains (Figure 3) which run along the a-
axis within the crystal lattice.
To summarize, we have prepared four new amide func-
tionalized ditertiary phosphines in good to excellent yields
and demonstrated their coordination behavior towards a
ꢁ
P(2)–Pt(1)–Cl(1) ranged between 170.95(4)–176.91(14) ].
III
Ligands 3a–d coordinate via both P donor atoms forming
II
typically soft metal center, in this case Pt .
six-membered Pt–P – C–N – C–P chelate rings [the bite angle
ꢁ
ranged between 92.96(3) and 95.88(7) ].
One noticeable solid state structure difference between
3. Experimental
4
aꢀ0.2(CHCl )ꢀ0.8(C H OS), 4bꢀ2(CHCl ), 4c and 4d, as evident
3
2
6
3
from single crystal X-ray studies, is the orientation of the planar All reactions, using reagent grade quality solvents, were
aromatic group on the N-alkyl backbone with respect to the carried out in air except the syntheses of 3a–d which were con-
4
platinum(II) center. Compounds 4c and 4d were found to con- ducted under an inert atmosphere. The compounds PtCl
(g -
2
[
12]
[13]
tain one intramolecular N(2)–H(2)ꢀꢀꢀN(1) H-bond [N(2)ꢀꢀꢀN(1) cod) (cod ¼ cycloocta-1,5-diene)
and HOCH
PPh
were
2
2
2
.723(15) and 2.704(9) Å; H(2)ꢀꢀꢀN(1) 2.45(14) and 2.26 Å; prepared according to literature methods. All other chemicals

4
M. R. J. ELSEGOOD ET AL.
Figure 3 Packing plot showing the N(2)–H(2)ꢀꢀꢀCl(1A) intermolecular chains in 4bꢀ2(CHCl
crystallisation are removed for clarity. Symmetry operator: A ¼ x þ 1, y, z.
3
). Hydrogen atoms not involved in H-bonding and solvent molecules of
Table 3. Crystallographic data for 4aꢀ0.2(CHCl
3
)ꢀ0.8(C
4aꢀ0.2(CHCl )ꢀ0.8 (C
OP
)ꢀ 0.8(C
899.00
Monoclinic
P2 /n
2
H
6
OS), 4bꢀ2(CHCl
3
), 4c and 4d.
Compound
3
2
H
6
OS)
4bꢀ2(CHCl
3
)
4c
4d
Empirical formula
C
34
H
32Cl
2
N
2
2
Pt
OS)
C
38
H34Cl
2
N
2
OP
2
Ptꢀ2(CHCl
3
)
C
41
H
2
36Cl N
2
OP
2
Pt
C
42
H
2
39Cl N
3
OP
2
Pt
ꢀ
0.2(CHCl
3
2
H
6
Formula weight
Crystal system
Space group
a [Å]
1101.34
Orthorhombic
P2
900.65
Monoclinic
P2 /c
929.69
Orthorhombic
Pnma
28.768(2)
17.1489(15)
8.0686(7)
1
1
2 2
1 1
1
10.3997(5)
46.949(2)
22.9518(11)
10.0491(6)
15.0403(9)
27.6518(16)
16.690(4)
14.838(3)
16.087(3)
b [Å]
c [Å]
a [˚]
b [˚]
93.394(2)
117.831(3)
c [˚]
Volume [Å ]
3
11186.7(9)
12
0.71073
150(2)
1.601
4179.3(4)
4
0.6719
150(2)
1.750
3.41
3523.1(13)
4
0.8462
150(2)
1.698
6.62
3980.6(6)
4
0.71073
150(2)
1.551
3.78
Z
k
T [K]
3
Density (calcd.) [Mg/m ]
Absorption coeff. [mm
–1
]
4.11
Crystal habit and color
Crystal size [mm ]
h Range [˚]
Plate, colorless
Rod, colorless
Lath, colorless
Plate, colorless
3
0.16 ꢃ 0.12 ꢃ 0.01
0.14 ꢃ 0.08 ꢃ 0.06
0.15 ꢃ 0.05 ꢃ 0.02
0.27 ꢃ 0.20 ꢃ 0.04
1.8-25.0
2.7–31.2
3.7–33.0
1.9–29.2
Reflections collected
81369
35749
25508
22777
Independent reflections
19717 [Rint ¼ 0.108]
14123 [Rint ¼ 0.043]
7430 [Rint ¼ 0.077]
5064 [Rint ¼ 0.034]
2
2
Reflections with F > 2r(F )
12921
13926
5967
4086
Number of parameters
1295
488
0.029, 0.079
447
0.072, 0.221
394
0.036, 0.094
a
b
Final R , wR2
0.075, 0.163
P
P
P
P
a
b
2
2 2
2 2 1/2
R ¼ jjF
o
j - jF
c
jj/ jF
o
j. wR2 ¼ [ [w(F
o
- F
c
) ]/ [w(F
o
) ]]
.
were obtained from commercial suppliers and no further
purification steps undertaken prior to use.
Details of the data collection parameters and crystal data for
4aꢀ0.2(CHCl )ꢀ0.8(C OS), 4bꢀ2(CHCl ), 4c and 4d are given
Measurements for 4aꢀ0.2(CHCl )ꢀ0.8(C OS),
), 4c and 4d were made on either a Bruker SMART
H
3
2
6
3
[
14 –17]
Infrared spectra were recorded as KBr pellets on either in Table 3.
H
2 6
3
–
1
a Perkin-Elmer System 2000 (4000–400 cm range) or a 4bꢀ2(CHCl
3
–
1
1
000 CCD (4aꢀ0.2(CHCl )ꢀ0.8(C H OS) and 4d; graphite mono-
Spectrum 100S (4000–250 cm range) Fourier-Transform
3
2 6
1
chromation and sealed tube Mo-K source) or Bruker APEX 2
spectrometer. H NMR spectra (400 MHz) were recorded on a
a
CCD (4bꢀ2(CHCl ) and 4c; silicon 111 monochromation and
3
Bruker DPX-400 FT spectrometer with chemical shifts (d) in
ppm to high frequency of Si(CH ) and coupling constants (J)
synchrotron radiation) diffractometers. Narrow frame x–scans
were employed and intensities were corrected semi-empirically
for absorption, based on symmetry-equivalent and repeated
reflections. The structures were solved by direct methods and
3
4
3
1
1
in Hz. P{ H} NMR spectra were recorded on a Bruker DPX-
00 FT spectrometer with chemical shifts (d) in ppm to high
frequency of 85% H PO . NMR spectra were measured in
4
3
4
2
refined on F values for all unique data by full-matrix least
CDCl at 298 K. Elemental analyses (Perkin-Elmer 2400 CHN
3
squares. The structures were solved routinely except as explained
or Exeter Analytical, Inc. CE-440 Elemental Analyzers) were
performed by the Loughborough University Analytical Service
within the Department of Chemistry. Mass spectra were
recorded within the Department of Chemistry at
as follows: in 4aꢀ0.2(CHCl )ꢀ0.8(C H OS) there were indications
3
2 6
of twinning, but no viable twin law could be determined. The
asymmetric unit contains three similar Pt complexes two fully
occupied DMSO molecules and a further site with part DMSO
Loughborough University and by the EPSRC National Mass (39.4(9)%) and part CHCl3 (0.606(9)%); 4bꢀ2(CHCl ) was
3
Spectrometry Service at Swansea University.
refined as an inversion twin with occupancy ratio 0.572:0.428(5);

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
5
4
c was refined as a two component twin with major component
Bis(diphosphine) Complexes. Chem. Commun. (Camb.) 2016,
2, 9343–9346.
5
contribution of 97.27(10)%; 4d lies on a mirror plane. The R
group at C(17) was multiply disordered. This group either lies
with the aromatic rings on the mirror or with this group perpen-
dicular to the mirror and hence protruding either to the left or
right of the mirror. There was some evidence of underlying twin-
ning, which could not be resolved.
Preparation of ditertiary phosphine 3a. Under a nitrogen
atmosphere, a solution of amine 2a (0.108 g, 0.719 mmol)
and Ph PCH OH (0.365 g, 1.52 mmol) in MeOH (20 mL)
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was stirred for 23 h at room temperature. The resulting solu-
tion was concentrated to ca. 5 mL under reduced pressure
and the resulting cream precipitate filtered and dried under
reduced pressure. Yield: 0.252 g, 64%. All other preparations
followed this general procedure and yields/selected charac-
terizing data are given in Table 1.
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Preparation of cis-PtCl (3a) 4a. Ligand 3a (0.091 g,
2
4
0
.17 mmol) was added to a stirred solution of PtCl (g -cod)
2
(
0.062 g, 0.17 mmol) in CH Cl (20 mL). The solution was
2 2
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stirred for 0.5 h and the solvent concentrated to ca. 2 mL
under reduced pressure. Diethyl ether (25 mL) was added
and the resulting solid stirred for a further 0.5 h. The pre-
cipitate was filtered and dried under reduced pressure.
Yield: 0.132 g, 97%. All other preparations followed this gen-
eral procedure and yields/selected characterizing data are
given in Table 1.
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a
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1
[
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Gonz ꢀa lez, A. M.; Maneiro, M.; Pedrido, R. J. Chem. Soc., Dalton
Trans. 2000, 3122–3127. (b) Bermejo, M. R.; Gonz ꢀa lez, A. M.;
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Acknowledgements
Johnson Matthey are gratefully acknowledged for the loan of precious
metal salts. The EPSRC Mass Spectrometry Service (Swansea
University) is acknowledged for data collection. CCLRC are thanked
for beam time at Daresbury Laboratory.
Funding
[
12] McDermott, J. X.; White, J. F.; Whitesides, G. M. Thermal
Decomposition of Bis(phosphine)Platinum(II) Metallocycles. J.
Am. Chem. Soc. 1976, 98, 6521–6528.
We would like to thank the EPSRC and Loughborough University for
funding (AJL).
[
13] Hellman, H.; Bader, J.; Birkner, H.; Schumacher, O.
Hydroxymethyl-Phosphine, Hydroxymethyl-Phosphoniumsalze
Und Chlormethyl-Phosphoniumsalze. Justus Liebigs Ann. Chem.
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