Syntheses and coordination chemistry of aminomethylphosphine derivatives of adenine

Article abstract of DOI:10.1002/ejic.200300037

Two aminomethylphosphane derivatives of adenine 9-(2-{bis[(diphenylphosphanyl)methyl]amino}ethyl)adenine (La) and 9-(3-{bis[(diphenylphosphanyl)methyl]amino}propyl)adenine (Lb) were synthesised. Oxidation of La and Lb with H₂O₂, elemental sulfur or elemental selenium led to the corresponding oxidized products 4a/b-6a/b. Both La and Lb behave as didentate ligands towards late transition metals. Reaction of La or Lb with [MX₂(cod)] (M = Pd, Pt; X = Cl, Me) gave chelate complexes 7a/b-10a/b. Reaction of La or Lb with [AuCl(tht)] of [{RuCl(μ-Cl)(p-MeC₆H₄iPr)}₂] gave the didentate bridging complexes 11a/b and 12a. All compounds have been fully characterised by microanalysis, IR, ¹H and ³¹P{¹H} NMR spectroscopy, and EI/CI/FAB mass spectrometry. ¹H{³¹P} NMR and ¹H-¹³C correlation experiments were used to confirm the spectral assignments where necessary. Two compounds were structurally characterised by X-ray crystallographic analysis. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejic.200300037

FULL PAPER
Syntheses and Coordination Chemistry of Aminomethylphosphine
Derivatives of Adenine
Qingzhi Zhang,[a] Guoxiong Hua,[a] Pravat Bhattacharyya,[a] Alexandra M. Z. Slawin,[a] and
J. Derek Woollins*[a]
Keywords: Adenine / P ligands / Chelate complexes / Heterometallic complexes
Two aminomethylphosphane derivatives of adenine 9-(2-
didentate bridging complexes 11a/b and 12a. All compounds
{bis[(diphenylphosphanyl)methyl]amino}ethyl)adenine (La)
have been fully characterised by microanalysis, IR, 1H and
and
9-(3-{bis[(diphenylphosphanyl)methyl]amino}propyl)- 31P{1H} NMR spectroscopy, and EI/CI/FAB mass spectro-
adenine (Lb) were synthesised. Oxidation of La and Lb with
H2O2, elemental sulfur or elemental selenium led to the cor-
responding oxidized products 4a/b−6a/b. Both La and Lb be-
metry. 1H{31P} NMR and 1H-13C correlation experiments
were used to confirm the spectral assignments where
necessary. Two compounds were structurally characterised
have as didentate ligands towards late transition metals. Re- by X-ray crystallographic analysis.
action of La or Lb with [MX2(cod)] (M = Pd, Pt; X = Cl, Me)
gave chelate complexes 7a/b−10a/b. Reaction of La or Lb
with [AuCl(tht)] or [{RuCl(µ-Cl)(p-MeC6H4iPr)}2] gave the
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
Introduction
trimethylene linkage at the 9-position. The adenine ana-
logues prepared in this way possess two functions: an
excellent coordination tendency toward transition metals
and the capacity for base-pair or complementary hydrogen-
bonding interactions. Some enhanced biological activities
are expected from the new combination of the bioactive ad-
enine and aminophosphane as well as the corresponding
complexes.
Owing to their resemblance to the structure of adenosine
and their broad-spectrum of antiviral or anticancer activity,
adenine derivatives substituted at the 9-position constitute
an important class of pharmacologically active com-
pounds.[1] Among them 9-[2-(phosphonomethoxy)ethyl]ad-
enine and its analogues have been extensively studied.[2,3] In
bioinorganic chemistry, metal complexes capable of for-
ming complementary hydrogen bonds occupy an increas-
ingly important position in the development of biochemi-
cally active molecules. Houlton et al.[4] have prepared some
interesting bifunctional complexes that combine the coval-
ent bond-forming capabilities of the metal ion and a ligand
surface capable of recognizing nucleotide bases by means of
hydrogen bonding. The same group developed the concept
of directed metallation and reported a series of nucleoside
Results and Discussion
Preparation and Oxidation of La and Lb
Scheme 1 shows the synthesis of La and Lb and the cor-
responding oxidized compounds. Precursor 1a was pre-
pared using 1-bromo-2-chloroethane and the sodium salt
of adenine, formed from adenine and sodium hydride in
anhydrous DMF by a literature method,[13,14] while 1b was
prepared following a modified literature method using ad-
enine and 1-bromo-3-chloropropane in the presence of an-
hydrous K2CO3 in anhydrous DMF, which proved to be
milder than NaH and gave a higher yield of the target
product.[15Ϫ17] Compounds 2[18] and 3[19] were also pre-
pared according to the literature method, with slight modi-
fication.
Due to the low solubility of 3a and 3b in common or-
ganic solvents at room temperature, the condensation reac-
tions with Ph2PCH2OH were carried out in refluxing aceto-
nitrile. Monitoring by 31P{1H} NMR spectroscopy indi-
cated that the reaction of 3a or 3b with a slight excess of
Ph2PCH2OH (3: Ph2PCH2OH ഠ 1:2 molar ratio) gave La
analogues in which the ribose group is replaced by a di-
methylene/trimethylene tethered ethylenediamine
[5Ϫ8]
or
1,2-dithioethane.[9] Interaction of such chelate-tethered nu-
cleoside analogues with metal ions gave interesting AϪN3-
bound or AϪC8-bound mono- or polynuclear complexes.
In an approach which combines the antitumour activities
of diphosphanes and their gold complexes[10,11] and our ex-
perience in the synthesis coordination chemistry of
PϪCϪN compounds,[12] we have incorporated the amino-
methylphosphane unit into adenine through an aminodi/
[a]
Department of Chemistry, University of St Andrews,
Fife, Scotland KY16 9ST, UK
Fax: (internat.) ϩ44-1334/463-384
E-mail: jdw3@st-and.ac.uk
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DOI: 10.1002/ejic.200300037
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Aminomethylphosphine Derivatives of Adenine
FULL PAPER
days only gives about 20% oxidation of the starting mate-
rial.
Characterization of La, Lb and 1a/b؊6a/b
La, Lb and compounds 1b, 2b, 3b, 4a/bϪ6a/b were fully
characterised by multinuclear NMR spectroscopy, EI/CI/
FAB mass spectrometry, infrared spectrometry and micro-
analysis. All the compounds gave reasonable microanalysis
results apart from 4a and 4b, which showed slightly lower
carbon percentages than the calculated value due to the im-
purities described above. Their mass spectra show the mo-
lecular ions and the expected fragmentation pattern with
appropriate isotope distributions. The sulfur and selenium
species 5a/bϪ6a/b show the [M Ϫ S]ϩ and [M Ϫ Se]ϩ frag-
ment ions in their EIMS spectra. The corresponding
[M ϪO]ϩ ion was not observed for 4a/b. In the IR spectra,
all compounds display two broad medium intensity νNϪH
bands between 3349 and 3106 cmϪ1. The strong NϪH
bending absorption of the NH2 group and the stretching
Scheme 1. Preparation and oxidation of La and Lb; i) NaH (60%
in mineral oil) or K2CO3, anhydrous DMF, room temp.; ii)
ClCH2CH2Br or ClCH2CH2CH2Br, room temp., 48 h; iii) NaN3,
DMF, 80 °C, 24 h; iv) H2, 1 atm, Pd/C (10%), MeOH; v) absorption of the CϭN bond of the purine ring were ob-
served at around 1655 cmϪ1 and 1598 cmϪ1, respectively.
Compounds 2a/b show an νNϵN band at 2100 cmϪ1. Com-
pounds 4a and 4b display the νPϭO absorption at ca. 1178
and 1176 cmϪ1; the νPϭS and νPϭSe bands could not be
Ph2PCH2OH, CH3CN, reflux, overnight; vi) H2O2 (30%), 0 °C,
THF, room temp., 2 h; or S8/Se, THF, reflux, overnight
and Lb overnight. Workup by simple concentration and assigned unambiguously for 5a/b and 6a/b.
washing with Et2O removes the excess Ph2PCH2OH, and
The 31P{1H} NMR signals (Table 1 and 2) of La/b at
recrystallisation from CH3CN gave the air- and moisture- around δP ϭ Ϫ27 ppm are similar to other bis[(diphenyl-
stable white solids L in good yields. The successful selec- phosphanyl)methyl]amine compounds.[22] The dichalcogen-
tivity of NϪC bond formation at the dangling alkylamino ides 4a/b-6a/b show signals shifted to higher frequency at
group rather than the aryl C6ϪNH2 at the purine ring can ca. δP ϭ 29, 35 and 25 ppm compared with that of La/
be attributed to the difference in basicities of the two pri- b. Interestingly, the 31P{1H} NMR spectra of the selenium
mary amino groups. The alkylamino group at the 9-position species 6a/b not only show a central singlet of 92% intensity
is much more electron-rich than the amino group at the 6- with selenium satellites (1JP,Se ϭ 730 Hz)[23] but also a small
position, whose lone pair is highly delocalised in the elec- PϪP coupling (4JP,P ϭ 9 Hz) in the satellites. The latter is
tron-withdrawing purine ring. Attempts to get 9-{2- due to the inequivalence of the two phosphorus atoms aris-
[(diphenylphosphanyl)methylamino]ethyl}adenine and 9- ing from the Ph2P(Se)CH2NCH2P(77Se)Ph2 isotopomer.
{3-[(diphenylphosphanyl)methylamino]propyl}adenine by Similar PϪP couplings in the selenium satellites were also
using a 1:1 molar ratio of reagents failed; double conden- observed in Ph2P(Se)NHP(Se)Ph2 (2JP,P ϭ 29 Hz)[24] and
sation always occurred under these conditions.
Oxidation of La and Lb with excess elemental sulfur or
Ph2P(Se)OP(Se)Ph2 (2JP,P ϭ 44 Hz).[25]
The 1H NMR spectra of 1b[14,26] and 3b[27] in [D6]DMSO
selenium in THF gave the corresponding sulfides and selen- or [D6]DMSO ϩ D2O have been reported previously. In
ides. As shown by 31P{1H} NMR spectroscopy, however, order to compare the NMR spectra of the precursors and
there is always a trace of unidentified impurities (δP ഠ 40.6, the aminomethylphosphanes La and Lb, the same solvent
37.7 and 36.5 ppm for sulfides; δP ഠ 27.0 ppm for selenides) should be employed. However, catalytic oxidation (with
in the reaction mixture, implying that the PϪCϪN bond is either catalyst or irradiation) of PIII compounds by DMSO
not very robust under oxidation conditions. Attempts to get has been reported[21,28Ϫ30] and we have also observed the
rid of the impurities were not successful by either chroma- gradual oxidation of some aminophosphane compounds in
tography or recrystallisation. Oxidation of La and Lb with [D6]DMSO during spectral acquisition, therefore the em-
aqueous H2O2 (30%) needs to be performed with caution. ployment of [D6]DMSO for La and Lb was precluded. For
The oxidizing agent can only be used stoichiometrically or comparative purposes, in addition to the spectra in
slightly in excess, otherwise oxidation at the N1 position of [D6]DMSO, the 1H NMR spectroscopic data of 1؊3 in
the purine ring occurs as described previously[20,21] and as CDCl3 containing a few drops of [D6]DMSO were ac-
observed in the mass spectrum. Even so, using our method quired. The data of 1a, 2a and 3a will be reported else-
there are still some unidentified impurities (δP ഠ 30.9, 27.0 where, and those of 1b, 2b, 3b are listed in Table 3. In the
and 26.0 ppm) in the reaction mixture that are very difficult 1H NMR spectra the chemical shifts of the C6ϪNH2 group
to remove. Oxidation of La and Lb by air proved too slow and one of the CH groups of the purine ring (C2ϪH or
to be useful as a preparative technique. Stirring a solution C8ϪH) vary with solvent ([D6]DMSO, CDCl3 or CDCl3/
of La or Lb in THF in air at room temperature for four [D6]DMSO). On the other hand, in the 13C{1H} NMR
Eur. J. Inorg. Chem. 2003, 2426Ϫ2437
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Q. Zhang, G. Hua, P. Bhattacharyya, A. M. Z. Slawin, J. D. Woollins
FULL PAPER
Table 1. NMR spectroscopic data for compounds La and 4aϪ6a
Entry
31P{1H} NMR (CDCl3)
1H NMR (CDCl3)
13C{1H} NMR (CDCl3)
δP (ppm)
J (Hz)
δH (ppm)
J (Hz)
δC (ppm)
J (Hz)
155.89 (C6)
152.98 (C2)
8.32 (s, 1 H, C2-H)
7.10 (s, 1 H, C8-H)
150.10 (C4)
141.29 (C8)
7.37Ϫ7.28 (m, 20 H, ArH)
5.55 (br. s, 2 H, NH2)
4.05 (t, 2 H, AdeCH2CH2)
3.61 (d, 4 H, PCH2)
137.65 (d, ArCi)
133.43 (d, ArC°)
129.03 (d, ArCm)
128.81 (s, ArCp)
119.54 (C5)
1JP,C ϭ 13
2JP,C ϭ 18
3JP,C ϭ 22
La
Ϫ26.71 (s)
3JCH,CH ϭ 6
4
2JP,CH or JP,CH ϭ 5
3.27 (t, 2 H, CH2NPCH2)
3JCH,CH ϭ 6
3
59.71 (dd, PCH2)
56.00 (t, CH2NPCH2)
42.16 (s, AdeCH2CH2)
154.20 (C6)
1JP,C ϭ 6, JP,C ϭ 8
3JP,C ϭ 9
8.24 (s, 1 H, C2-H)
7.60 (s, 1 H, C8-H)
7.70Ϫ7.31 (m, 20 H, ArH)
6.87 (v br. s, 2 H, NH2)
4.19 (t, 2 H, AdeCH2CH2)
3.82 (d, 4 H, PCH2)
152.22 (C2)
150.19 (C4)
142.24 (C8)
4a
5a
6a
29.06 (s)
35.37 (s)
25.26 (s)
132.47Ϫ128.20 (m, PhC)
119.15 (C5)
3JCH,CH ϭ 6
4
2JP,CH or JP,CH ϭ 5
57.92 (t, CH2NPCH2)
56.67 (dd, PCH2)
41.83 (s, AdeCH2CH2)
154.91 (C6)
3JP,C ϭ 6
1JP,C ϭ 82,3JP,C ϭ 7
3.50 (t, 2H CH2NPCH2)
3JCH,CH ϭ 6
8.25 (s, 1 H, C2-H)
7.85 (s, 1 H, C8-H)
7.83Ϫ7.36 (m, 20 H, ArH)
5.93 (br. s, 2 H, NH2)
4.19 (br. s, 4 H, PCH2)
4.07 (t, 2 H, AdeCH2CH2)
3.43 (t, 2 H, CH2NPCH2)
151.98 (C2)
149.99 (C4)
142.03 (C8)
132.48Ϫ128.65 (m, PhC)
119.51 (C5)
3JCH,CH ϭ 6
3JCH,CH ϭ 6
59.34 (d, PCH2)
56.40 (br. s CH2NPCH2)
42.58 (s, AdeCH2CH2)
155.34 (C6)
1JP,C ϭ 58
8.24 (s, 1 H, C2-H)
7.88 (s, 1 H, C8-H)
7.78Ϫ7.35 (m, 20 H, ArH)
6.10 (br. s, 2 H, NH2)
4.41 (br. s, 4 H, PCH2)
3.99 (t, 2 H, AdeCH2CH2)
3.42 (t, 2 H, CH2NPCH2)
152.41 (C2)
149.80 (C4)
141.61 (C8)
1JP,Se ϭ 730
4JP,PЈ ϭ 9
132.10Ϫ128.74 (m, PhC)
119.41 (C5)
59.34 (d, PCH2)
56.11 (br. s, CH2NPCH2)
42.72 (s, AdeCH2CH2)
3JCH,CH ϭ 6
3JCH,CH ϭ 6
1JP,C ϭ 51
spectra, the resonance frequencies of the carbons (C2, C4, pears at relatively higher frequency. The proton signals of
C5, C6 and C8) of the purine ring of compounds 1؊3 show the dangling chain of La and 4a/6a are as easy to assign as
little variation in different solvents. To assign the C2ϪH their precursors 1aϪ3a, which will be reported elsewhere,
1
and C8ϪH protons unambiguously, H-13C heteronuclear with the triplet of AdeCH2CH2 at higher frequency be-
correlation spectra (HMQC) were measured. It turned out tween δH ϭ 4.48 and 4.05 ppm and the triplet of
that the C8ϪH appears at lower frequency at around δH
ϭ
CH2N(CH2PPh2) at lower frequency between δH ϭ 3.61
7.8 ppm in CDCl3 or CDCl3/[D6]DMSO, while in and 3.42 ppm. For Lb and 4b/6b, the triplet of AdeCH2CH2
[D6]DMSO, it is close to the C2ϪH resonance at around between δH
3.95 and 3.76 ppm and that of
H ϭ 8.2 ppm. The C6ϪNH2 resonance in CDCl3 or CDCl3 CH2N(CH2PPh2) between δH ϭ 3.09 and 2.79 ppm are at
ϩ [D6]DMSO is observed at around δH ϭ 5.6 ppm, while slightly lower frequency than in La and 4a/6a, but still fol-
in [D6]DMSO it appears at around δH ϭ 7.2 ppm. low the tendency AdeCH2CH2 Ͼ CH2N(CH2PPh2). The
ϭ
δ
Based on the above observation, we assign the higher fre- triplet of CH2N(CH2PPh2) seems always less-well resolved
quency singlet at δH ϭ 8.32Ϫ8.24 ppm to C2ϪH and the and slightly broader than that of AdeCH2CH2, which may
1
lower one at δH ϭ 7.10Ϫ7.88 ppm to C8 in the H NMR be attributed to the long-distance coupling of these methyl-
1
spectra of La/b and 4a/bϪ6a/b. The H-13C heteronuclear ene protons with phosphorus atoms. The AdeCH2CH2CH2
correlation experiment confirmed the assignments. Like signal in Lb and 4bϪ6b appears as a well-resolved quintet
their precursors 1؊3, the broad singlet of C6ϪNH2 of La, at an even lower frequency, between δH ϭ 1.87 and
Lb and 4؊6 appears at around δH ϭ 6 ppm. Among them, 1.69 ppm. The signal of CH2PPh2 of the above compounds
the resonance of C6ϪNH2 of the oxygen species 4a/b ap- appears between δH ϭ 4.47 and 3.60 ppm as a doublet or
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Aminomethylphosphine Derivatives of Adenine
FULL PAPER
Table 2. NMR spectroscopic data for compounds Lb and 4bϪ6b
Entry 31P{1H} NMR (CDCl3)
1H NMR (CDCl3)
13C{1H} NMR (CDCl3)
δP (ppm)
J (Hz)
δH (ppm)
J (Hz)
δC (ppm)
J (Hz)
155.45 (C6)
8.30 (s, 1 H, C2-H)
152.82 (C2)
7.25 (s, 1 H, C8-H)
150.19 (C4)
7.44Ϫ7.25 (m, 20 H, ArH)
5.74 (br. s, 2 H, NH2)
3.81 (t, 2 H, AdeCH2CH2)
3.60 (d, 4 H, PCH2)
2.79 (t, 2 H, CH2NCH2P)
1.83 (quint, 2 H, AdeCH2CH2)
141.33 (C8)
Lb
Ϫ28.12 (s)
137.94 (d, ArCi)
133.38 (d, ArCo)
1JP,C ϭ 12
2JP,C ϭ 19
3JP,C ϭ 21
3JCH,CH ϭ 6
2JP,CH or JP,CH ϭ 3 128.80 (d, ArCm)
4
3JCH,CH ϭ 6
128.74 (s, ArCp)
119.97(C5)
3
59.01 (dd, PCH2)
53.18 (t, CH2NCH2P)
41.70 (s, AdeCH2CH2)
17.30 (s, AdeCH2CH2)
154.48 (C6)
1JP,C ϭ 6 or 9 JP,C ϭ 6 or 9
3JP,C ϭ 9
8.29 (s, 1 H, C2-H)
7.58 (s, 1 H, C8-H)
150.31 (C2)
149.67 (C4)
141.80 (C8)
7.85Ϫ7.36 (m, 20 H, ArH)
6.78 (v br. s, 2 H, NH2)
4b
5b
6b
29.43(s)
35.27 (s)
24.64 (s)
132.79Ϫ128.19 (m, PhC)
4
3.76 (d ϩ t, 6 H, PCH2ϩ AdeCH2) 2JP,CH or JP,CH ϭ 5 119.65 (C5)
3
3.09 (t, 2 H, CH2NCH2P)
1.87 (quint, 2 H, AdeCH2CH2)
3JCH,CH ϭ 6
3JCH,CH ϭ 6
56.07 (dd, PCH2)
55.75 (t, CH2NCH2P)
42.27 (s, AdeCH2CH2)
27.46 (s, AdeCH2CH2)
155.25 (C6)
1JP,C ϭ 83, JP,C ϭ 7
3JP,C ϭ 7
8.30 (s, 1 H, C2-H)
7.70 (s, 1 H, C8-H)
152.38 (C2)
150.12 (C4)
7.87Ϫ7.32 (m, 20 H, ArH)
5.84 (br. s, 2 H, NH2)
4.29 (br. s, 4 H, PCH2)
3.95 (t, 2 H, AdeCH2CH2)
2.95 (t, 2 H, CH2NCH2P)
1.76 (quint, 2 H, AdeCH2CH2)
141.36 (C8)
132.76Ϫ128.74 (m, PhC)
119.87 (C5)
57.96 (d, PCH2)
3JCH,CH ϭ 7
3JCH,CH ϭ 7
3JCH,CH ϭ 7
1JP,C ϭ 62
53.56 (br. t, CH2NCH2P) 3JP,C ϭ 4
41.74 (s, AdeCH2CH2)
27.02 (s, AdeCH2CH2)
155.22 (C6)
8.29 (s, 1 H, C2-H)
7.72 (s, 1 H, C8-H)
152.42 (C2)
150.15 (C4)
7.88Ϫ7.30 (m, 20 H, ArH)
141.16 (C8)
1JP,Se ϭ 730 5.88 (br. s, 2 H, NH2)
132.18Ϫ128.80 (m, PhC)
119.99 (C5)
57.67 (d, PCH2)
53.13 (t, CH2NCH2P)
41.69 (s, AdeCH2CH2)
27.26 (s, AdeCH2CH2)
4JP,PЈ ϭ 9
4.47 (br. s, 4 H, PCH2)
3.95 (t, 2 H, AdeCH2CH2)
2.92 (t, 2 H, CH2NCH2P)
1.69 (quint, 2 H, AdeCH2CH2)
3JCH,CH ϭ 7
3JCH,CH ϭ 7
3JCH,CH ϭ 7
1JP,C ϭ 52
3JP,C ϭ 4
1
3
broad singlet arising from the two-bond or four-bond coup- to the JP,C and/or JP,C couplings, appears at the highest
lings of CH and phosphorus. This resonance can appear frequency in the alkyl region. La and Lb exhibit neat signals
at a higher or lower frequency than, and sometimes even in the aromatic carbon region and the coupling constants
overlapped with, that of AdeCH2CH2.
nJP,C (n ϭ 1, 2, 3) are available in Table 1 and 2. The coup-
n
In the 13C{1H} NMR spectra, La/Lb and their oxidized ling constants JP,C (n ϭ 1, 2, 3) in 4a/b-6a/b, however, are
compounds show very similar purine ring carbon signals very difficult to observe due to the trace impurities that
(Table 1 and 2) to their precursors and other reported aden- cause small overlapping signals in the aromatic carbon res-
ine analogues.[31] However, as revealed by a H-13C hetero- onance region in 4a/b-6a/b.
1
nuclear correlation experiment, the 13C signal of
Compound 2b was also characterised by X-ray crystal-
CH2NCH2PPh2 is shifted to higher frequency between lography (Figure 1 and Table 4). Two typical types of hy-
δC ϭ 57.92 and 53.13 ppm and appears as a triplet or broad drogen bonding for the purine system are observed between
singlet due to coupling with the phosphorus atoms, while adjacent molecules (Figure 1, bottom), they are the
the signal of AdeCH2CH2 remains as a singlet between WatsonϪCrick type between N(6)ϪH of one molecule and
δC ϭ 42.58 and 41.69 ppm. The CH2PPh2 signal, which ap- N(1) of a second molecule, [N(6)ϪH(6A)···N(1A), d(D···A)
˚
˚
pears as a doublet of doublets, doublet or broad singlet due 3.056(4) A, d(H···A) 2.10 A, Є(DHA) 164(2)°], and the
Eur. J. Inorg. Chem. 2003, 2426Ϫ2437
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Q. Zhang, G. Hua, P. Bhattacharyya, A. M. Z. Slawin, J. D. Woollins
FULL PAPER
Table 3 NMR spectroscopic data for compounds 1bϪ3b
Entry
1H NMR ([D6]DMSO)
1H NMR (CDCl3 for 1b, 2b;
CDCl3 ϩ [D6]DMSO for 3b)
δH (ppm)
13C{1H} NMR
([D6]DMSO)
δC (ppm)
13C{1H} NMR (CDCl3 for 1b, 2b;
CDCl3 ϩ [D6]DMSO for 3b)
δC (ppm)
δH (ppm)
J (Hz)
J (Hz)
155.96 (C6)
155.30 (C6)
8.16 (s, 1 H, C8-H)
8.15 (s, 1 H, C2-H)
7.22 (br. s, 2 H, NH2)
4.30 (t, 2 H, AdeCH2CH2)
3.65 (t, 2 H, CH2Cl)
2.31 (quint, 2 H,
8.38 (s, 1 H, C2-H)
152.41 (C2)
153.49 (C2)
7.85 (s, 1 H, C8-H)
149.52 (C4)
150.08 (C4)
5.55 (br. s, 2 H, NH2)
4.43 (t, 2 H, AdeCH2CH2)
3.53 (t, 2 H, CH2Cl)
140.78 (C8)
141.20 (C8)
1b
3JCH,CH ϭ 6
3JCH,CH ϭ 6
3JCH,CH ϭ 6
3JCH,CH ϭ 6
3JCH,CH ϭ 6
3JCH,CH ϭ 6
118.76 (C5)
119.82 (C5)
42.33 (AdeCH2CH2)
40.58 (CH2Cl)
41.67 (AdeCH2CH2)
41.33 (CH2Cl)
2.40 (quint, 2 H, AdeCH2CH2)
AdeCH2CH2)
31.99 (AdeCH2CH2)
155.91 (C6)
32.19 (AdeCH2CH2)
155.73 (C6)
8.37 (s, 1 H, C2-H)
7.81 (s, 1 H, C8-H)
5.91 (br. s, 2 H, NH2)
4.32 (t, 2 H, AdeCH2CH2)
3.36 (t, 2 H, CH2N3)
2.18 (quint, 2 H,
152.92 (C2)
153.35 (C2)
8.16 (s, 2 H, C8-H ϩ C2-H)
7.21 (br. s, 2 H, NH2)
4.27 (t, 2 H, AdeCH2CH2)
3.39 (t, 2 H, CH2Cl)
2.08 (quint, 2 H,
149.53 (C4)
150.33 (C4)
140.73 (C8)
140.77 (C8)
2b
3JCH,CH ϭ 7
3JCH,CH ϭ 7
3JCH,CH ϭ 7
3JCH,CH ϭ 7
3JCH,CH ϭ 7
3JCH,CH ϭ 7
118.74 (C5)
120.05 (C5)
48.12 (CH2N3)
40.53 (AdeCH2CH2)
48.38 (CH2N3)
41.24 (AdeCH2CH2)
AdeCH2CH2)
AdeCH2CH2)
28.63 (AdeCH2CH2)
155.92 (C6)
29.26 (AdeCH2CH2)
155.64 (C6)
8.21 (s, 1 H, C2-H)
152.29 (C2)
152.91 (C2)
8.14 (s, 2 H, C2-H ϩ C8-H)
7.20 (br. s, 2 H, NH2)
4.21 (t, 2 H, AdeCH2CH2)
2.48 (t, 2 H, CH2NH2)
1.86 (quint, AdeCH2CH2)
1.54 (br. s, 2 H, NH2)
7.73 (s, 1 H, C8-H)
149.54 (C4)
150.14 (C4)
3b
5.85 (br. s, 2 H, NH2)
4.20 (t, 2 H, AdeCH2CH2)
2.57 (t, 2 H, CH2NH2)
1.89 (quint, AdeCH2CH2)
1.13 (br. s, NH2)
140.88 (C8)
140.58 (C8)
3JCH,CH ϭ 7
3JCH,CH ϭ 7
3JCH,CH ϭ 7
3JCH,CH ϭ 7
3JCH,CH ϭ 7
3JCH,CH ϭ 7
118.70 (C5)
119.60 (C5)
40.54 (AdeCH2CH2)
38.43 (CH2NH2)
33.27 (AdeCH2CH2)
40.91 (AdeCH2CH2)
38.52 (CH2NH2)
33.48 (AdeCH2CH2)
1
Hoogsteen type between the other N(6)ϪH of this molecule ling (3416 Hz) and the relatively small JPt,P coupling (ca.
and N(7) of a third molecule [N(6)ϪH(6B)···N(7B), 1782 Hz) are typical of a phosphorus trans to a chloride
˚
˚
d(D···A) 3..082(3) A, d(H···A) 2.11 A, Є(DHA) 174(4)°].
and a methyl group, respectively, and are thus in agreement
with the cis-geometry. Complex 10a/b displays two doublets
(2JP,P ഠ 22 Hz) corresponding to the two inequivalent phos-
phorus atoms. The doublet at ca. δP ϭ 4.0 ppm with a large
1JPt,P coupling of ca. 4200 Hz was assigned to the phos-
phorus trans to chloride and the signal with a small JPt,P
of about 1640 Hz at ca. δP ϭ 0.8 ppm to the phosphorus
atoms trans to the methyl group.
Coordination Chemistry of La/b with Late Transition
Metals
As shown in Scheme 2, La/b are excellent didentate li-
gands towards late transition metals. Reaction of La/b with
[MX2(cod)] gave a series of didentate complexes 7a/b؊10a/
b. Interaction of La/b with two molar equivalents of
[AuCl(tht)] gave the didentate bridging bimetallic com-
1
The 1H NMR spectra of the complexes in CD2Cl2 or
plexes 11a/b. The reaction of La and [{RuCl2(η6-p- CDCl3 (Table 5) are generally similar to that of the free li-
MeC6H4iPr)}2] also gave the bimetallic compound 12a. All gand La/b, the chemical shifts of C2ϪH (δH ഠ 8.2 ppm) Ͼ
the complexes gave reasonable microanalyses. Their FAB- C8ϪH (δH ഠ 7.0 ppm) and that of AdeCH2 (δH ഠ 3.7 ppm)
MS or ES-MS spectra show the expected molecular ion and Ͼ CH2NCH2P (δH ഠ 3.0 ppm). Like La/b, the chelate com-
fragmentation ions, with appropriate isotope distribution. plexes show a doublets of doublet, a doublet or a broad
2
4
In the IR spectra the anticipated medium intensity νNϪH singlet for CH2P, arising from JP,CH and/or JP,CH coup-
stretching band at around 3395Ϫ3314 cmϪ1 and ling, between the signals of AdeCH2 and CH2NCH2P, ex-
3186Ϫ3144 cmϪ1, and the very strong νNϪH bending and cept complex 9b, while the CH2P signal in the bridging
νCϭN stretching at around 1637 cmϪ1 and 1596 cmϪ1
,
complexes 11a/b and 12a appears at higher frequency than
respectively, were observed as in the free ligands and oxid- that of AdeCH2. The platinum complexes display satellites
ized compounds. In the complexes, medium intensity νMϪCl for both CH2P and the coordinated CH3 groups. The coup-
vibrations were also observed at 329Ϫ246 cmϪ1; the two ling constants JPtCH ഠ 38 Hz for the dichloride com-
3
3
3
bands in this region for complexes 7a/b, 8a/b are in agree- pounds 8a/b, JPtCH ഠ 15 Hz for 9a/b, and JPtCH ϭ 45
ment with the cis-geometry of the chelate complexes. and 15 Hz for 10a/b were obtained unambiguously from the
The 31P{1H} NMR spectra of 7a/bϪ10a/b (Table 5) show 1H{31P} NMR spectra. The doublet of doublets for CH3 at
high-frequency shifts relative to the free ligands. The plati-
H ϭ 0.33 and 0.49 ppm with satellites (2JPt,CH ϭ 54 Hz) in
δ
num species gave more information because of the platinum 10a/b can be easily interpreted as being due to the coupling
1
satellites. In complexes 8a/b and 9a/b the large JPt,P coup- of this group with the two inequivalent phosphorus atoms.
2430
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2003, 2426Ϫ2437

Aminomethylphosphine Derivatives of Adenine
FULL PAPER
Figure 1. (top) The crystal structure of 9-(3-azidopropyl)adenine (2b); (bottom) the crystal structure of 2b showing part of the hydro-
gen bonding
However, the two peaks at δH ϭ 0.39 ppm with satellites
(2JPt,CH ഠ 68 Hz) in 9a/b are somewhat confusing. The
˚
Table 4. Selected bond lengths (A) and angles (°) in compound 2b
1H{31P} NMR spectra reveal that the signals are not from
C(2)ϪN(1)
C(4)ϪN(3)
C(6)ϪC(5)
C(6)ϪN(6)
C(8)ϪN(7)
N(9)ϪC(4)
C(11)ϪC(10)
C(12)ϪN(13)
N(14)ϪN(15)
1.340(3)
1.348(3)
1.395(4)
1.340(3)
1.306(3)
1.373(3)
1.492(4)
1.450(5)
1.117(4)
N(3)ϪC(2)
C(5)ϪC(4)
N(1)ϪC(6)
N(7)ϪC(5)
N(9)ϪC(8)
C(10)ϪN(9)
C(11)ϪC(12)
N(13)ϪN(14)
1.318(4)
1.378(4)
1.356(3)
1.399(7)
1.357(3)
1.457(3)
1.503(4)
1.226(4)
the inequivalent CH3 groups but are a doublet (3JP,CH
ഠ
2 Hz) due to the coupling of the equivalent methyl groups
with either a trans or a cis phosphorus atom; it is not clear
why only one coupling is observed.
Slow diffusion of petroleum ether (b.p. 60Ϫ80 °C) into a
solution of 10b in CH2Cl2 gave colourless crystals suitable
for X-ray analysis (Figure 2 and Table 6). Figure 2 (top)
reveals a platinum coordinated in a square plane with a
C(2)ϪN(1)ϪC(6)
C(4)ϪN(3)ϪC(2)
C(6)ϪC(5)ϪC(4)
N(7)ϪC(5)ϪC(4)
N(9)ϪC(8)ϪN(7)
C(5)ϪC(4)ϪN(9)
C(12)ϪC(11)ϪC(10)
N(14)ϪN(13)ϪC(12)
118.1(3)
N(3)ϪC(2)ϪN(1)
N(3)ϪC(4)ϪC(5)
N(1)ϪC(6)ϪC(5)
C(8)ϪN(7)ϪC(5)
C(4)ϪN(9)ϪC(8)
N(9)ϪC(10)ϪC(11)
N(13)ϪC(12)ϪC(11)
N(15)ϪN(14)ϪN(13)
130.5(3)
˚
maximum
deviation
of
0.04
A
for
the
109.6(2)
117.4(2)
110.0(2)
115.0(2)
106.5(2)
113.2(3)
117.0(3)
127.2(3)
117.3(3)
103.2(2)
105.2(2)
113.1(2)
111.8(3)
170.2(5)
P(14)ϪP(15)ϪC(40A)ϪCl(1A)ϪPt(1) mean plane. The six-
membered chelate ring is chair-like, with the
N(13)ϪC(14)ϪC(15) plane heavily folded above (72°) and
the P(14)ϪPt(1)ϪP(15) plane slightly below (15°) the mean
˚
plane P(14)ϪP(15)ϪC(14)ϪC15) (mean deviation 0.03 A).
As shown in Figure 2 (bottom), both the WatsonϪCrick
˚
[N(6)ϪH(6A)···N(1A); d(D···A) 3.069(10) A, d(H···A)
Eur. J. Inorg. Chem. 2003, 2426Ϫ2437
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2431

Q. Zhang, G. Hua, P. Bhattacharyya, A. M. Z. Slawin, J. D. Woollins
FULL PAPER
Scheme 2. Coordination of La and Lb to transition metals; i) [MX2(cod)] (M ϭ Pd, Pt; X ϭ Cl, CH3), CH2Cl2, 2 h; ii) 2[AuCl(tht)],
CH2Cl2, 2 h
˚
mass spectra by the EPSRC Mass Spectrometer Service (Swansea,
UK). Precious metal salts were provided on loan by Johnson Mat-
they Plc.
2.12
A,
Є(DHA)
164
(4)°]
and
˚
Hoogsteen
[N(6)ϪH(6B)···N(7B); d(D···A) 3.04(10) A, d(H···A) 2.14
A, νDHA 152(6)°] types of intermolecular hydrogen bond-
˚
ing between adjacent molecules are found in the crystal. A
quarter molecule of solvate hexane was also observed. For
clarity, the solvate molecule is omitted from the figure.
9-(3-Chloropropyl)adenine (1b):[15Ϫ17] 1-Bromo-3-chloropropane
was added to adenine (27 g, 199.8 mmol) and anhydrous K2CO3
in anhydrous DMF (300 mL). The mixture was stirred under an
atmosphere of nitrogen for 4 days. The resultant suspension was
filtered and the residue was washed with CH2Cl2 (3 ϫ 30 cm3). The
combined filtrates were evaporated to dryness by rotary evapor-
ation. The crude product was washed by water (600 cm3) with son-
ication in an ultrasonic bath. Recrystallisation from ethanol (220
cm3) gave 28.0 g of the white product. The mother liquor was con-
centrated and recrystallised three times to give three additional
crops (5.92 g). Total yield: 33.92 g, 80.2%. C8H10ClN5 (211.7):
calcd. C 45.40, H 4.76, N 33.09; found C 45.79, H 4.54, N 33.34.
IR (KBr disc): ν˜ ϭ 3289m cmϪ1, 3114m, 1667vs, 1603vs. CIMS:
m/z ϭ 212 [M ϩ H]ϩ, 176 [M ϪCl]ϩ. EIMS: m/z ϭ 211 [M]ϩ, 176
[M Ϫ Cl]ϩ, 148 [M Ϫ CH2CH2Cl]ϩ.
Conclusion
We report here two [(diphenylphosphanyl)methyl]amino
analogues of adenosine La/b and their chalcogenide deriva-
tives. La and Lb proved to be good didentate ligands
towards late transition metals to give a series of didentate
chelate complexes and didentate bridging complexes. All
the compounds retain a free adenine moiety for comp-
lementary hydrogen bonding. Further studies on the inter-
action of these compounds with DNA and bioactivities
are underway.
9-(3-Azidopropyl)adenine (2b):[18] Compound 1b (20 g, 94.5 mmol)
and sodium azide (18.4 g, 283 mmol) were mixed in DMF (150
cm3). The mixture was stirred at 80 °C for 24 h, cooled to room
temperature and then filtered. The solid was washed with CH2Cl2
(3 ϫ 30 cm3). The combined filtrates were vacuumed to almost
dryness under rotary evaporation. The residue was taken up in H2O
(200 cm3) with sonication. The crude product was filtered off and
washed with water (3 ϫ 30 cm3). The combined aqueous layer was
extracted with CH2Cl2 (3 ϫ 600 cm3). Removal of the solvent from
the extracts led to another crop of crude product. The two crops
of crude product were recrystallised from EtOH (300 cm3) to gave
12.17 g of white solid. Further recrystallisation of the mother
liquor gave another 3.90 g of product. Total yield: 16.07 g, 77.7%.
C8H10N8 (218.9): calcd. C 44.03, H 4.62, N 51.35; found C 44.13,
H 4.44, N 52.06. IR (KBr disc): ν˜ ϭ 3302m cmϪ1, 3140s, 2108vs,
1664vs, 1600vs. CIMS: m/z ϭ 220 [M ϩ H]ϩ, 219 [M]ϩ, 191 [M Ϫ
N2]ϩ, 163 [M Ϫ CH2N3]ϩ, 136 [M Ϫ CH2CH2CH2N3]ϩ.
Experimental Section
General: All solvents and reagents were purchased from either Ald-
rich or Lancaster. Dichloromethane was heated to reflux over pow-
dered calcium hydride and distilled under nitrogen. Diethyl ether
and tetrahydrofuran were purified by reflux over sodium/benzo-
phenone and distillation under nitrogen. Ligand preparations were
performed under an oxygen-free nitrogen atmosphere using stand-
ard Schlenk techniques. Coordination reactions and workup were
performed in dry solvents. Ph2PCH2OH,[32] [MX2(cod)] (M ϭ Pd,
Pt; X ϭ Cl; cod ϭ cycloocta-1,5-diene)[33] and [AuCl(tht)] (tht ϭ
tetrahydrothiophene)[34] were prepared following literature pro-
cedures.
Infrared spectra were recorded as KBr discs on a PerkinϪElmer
system 2000 spectrometer. 1H NMR spectra (300 MHz) were re-
corded on a Varian Gemini 2000 spectrometer, 31P{1H} NMR
spectra at 121.4 MHz (referenced to external 85% H3PO4) and
13C{1H} NMR spectra at 67.9 MHz on a JEOL GSX 270 spec-
9-(3-Aminopropyl)adenine (3b):[19] 9-(3-Azidoproyl)adenine (10 g,
5.76 mmol) was dissolved in methanol (700 cm3). To this solution
was added palladium on carbon (10%, 5.0 g) and hydrogen gas was
bubbled in. Monitoring by TLC (SiO2, CH2Cl2/ MeOH ϭ 80:20)
trometer, and 1H{31P} NMR and 2D NMR (1H-13C heteronuclear showed that the reaction was complete after about 22 h. The cata-
correlation experiment) on a Bruker Advance 300. Microanalyses lyst was removed by filtration through celite. Solvent removal from
were performed by the University Service within this Department the filtrate by rotary evaporation gave the product as a white solid.
and fast atom bombardment (FAB) or chemical ionization (CI) Yield: 7.60 g, 83%. C8H12N6 (192.2): calcd. C 49.99, H 6.29,
2432
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2003, 2426Ϫ2437

Aminomethylphosphine Derivatives of Adenine
FULL PAPER
[a]
[b]
Table 5. NMR spectroscopic data in CD2Cl2 or CDCl3 for complexes of La and Lb
Entry NMR
δP (ppm) &
Entry NMR
δP (ppm) &
δH (ppm)
J (Hz)
δH (ppm)
δH (ppm)
J (Hz)
J (Hz)
8.22 (br. s, 1 H, C2-H)
7.79Ϫ7.39 (m, 20 H, PhH)
6.52 (br. s, 1 H, C8-H
5.67 (br. s, 2 H, NH2)
3.90 (t, 2 H, AdeCH2CH2)
3.46 (dd, 4 H, PCH2)
8.20 (br. s, 1 H, C2-H)
7.89Ϫ7.46 (m, 20 H, PhH)
7.37 (br. s, 1 H, C8-H)
5.46 (br. s, 2 H, NH2)
3.79 (t, 2 H,AdeCH2CH2)
3.42 (dd, 4 H, PCH2)
7a[a]
9.37 (s)
7b[a]
9.01 (s)
3JCH,CH ϭ 6
3JCH,CH ϭ 7
2JP,CH ϭ 3 or 5
4JP,CH ϭ 3 or 5
3JCH,CH ϭ 6
2JP,CH ϭ 3 or 5
4JP,CH ϭ 3 or 5
3JCH,CH ϭ 7
3.08 (t, 2 H, CH2NCH2P)
2.61 (t, 2 H, CH2NCH2P)
1.85 (quint, 2 H, AdeCH2CH2) 3JCH,CH ϭ 7
8.28 (br. s, 1 H, C2-H)
7.91Ϫ7.44 (m, 20 H, PhH)
7.25 (br. s, 1 H, C8-H)
8.02 (s, 1 H, C2-H)
7.81Ϫ7.33 (m, 20 H, PhH)
6.37 (s, 1 H, C8-H)
5.51 (br. s, 2 H, NH2)
3.74 (t, 2 H, AdeCH2CH2)
8a[a]
Ϫ7.07 (s)
1JPt,P ϭ 3416
5.61 (br. s, 2 H, NH2)
8b[b]
Ϫ7.13 (s)
1JPt,P ϭ 3416
3JCH,CH ϭ 7
4
3.90 (t, 2 H, AdeCH2CH2)
3.51 (d, 4 H, PCH2)
3JCH,CH ϭ 6
3.48 (d, 4 H, PCH2)
2JP,CH or JP,CH ϭ 3,
3JPt,CH ϭ 37
3JCH,CH ϭ 7
2JP,CH or
4JP,CH ϭ 3
3JPt,PCH ϭ 38
2.57 (t, 2 H, CH2NCH2P)
3.01 (t, 2 H, CH2NCH2P)
1.86 (quint, 2 H, AdeCH2CH2) 3JCH,CH ϭ 7
8.28 (s, 1 H, C2-H)
7.77Ϫ7.69 (m, 20 H, PhH)
6.83 (s, 1 H, C8-H)
5.47 (br. s, 2 H, NH2)
3.57 (d, 2 H, PCH2)
8.02 (s, 1 H, C2-H)
7.62Ϫ7.33 (m, 20 H, PhH)
5.90 (s, 1 H, C8-H)
9a[b]
2.21 (s)
1JPt,P ϭ 1782
5.68 (br. s, 2 H, NH2)
9b[b]
1.70 (s)
1JPt,P ϭ 1784
2JP,CH or JP,CH ϭ 3
4
3JPt,CH ϭ 16
3JCH,CH ϭ 7
3JCH,CH ϭ 7
3.83 (t, 2 H, AdeCH2CH2)
3.51 (br. s, 4 H, PCH2)
2.88 (t, 2 H, CH2NCH2P)
0.39 (d, 6 H, CH3)
3JCH,CH ϭ 6
3JPt,CH ϭ 14
3JP,H ϭ 2
3.38 (t, 2 H, AdeCH2CH2)
2.41 (t, 2 H, CH2NCH2P)
1.68 (quint, 2 H, AdeCH2CH2) 3JCH,CH ϭ 7
2JPt,H ϭ 68
0.39 (d, 6 H, CH3)
3JP,CH ϭ 2,
2JPt,CH ϭ 69
8.19 (s, 1 H, C2-H)
7.82Ϫ7.38 (m, 20 H, PhH)
7.11 (s, 1 H, C8-H)
5.42 (br. s, 2 H, NH2)
3.57 (t, 2 H, AdeCH2CH2)
3.52 (d, 2 H, PCH2)
8.20 (s, 1 H, C2-H)
7.72Ϫ7.20 (m, 20 H, PhH)
6.22 (s, 1 H, C8-H)
5.86 (br. s, 2 H, NH2)
3.85 (t, 2 H, AdeCH2CH2)
3JCH,CH ϭ 7
10a[a]
3.97 (d)
3JCH,CH ϭ 6
10b[a]
4.47 (d)
2JP,CH or JP,CH ϭ 3
4
1JPt,P ϭ 4169
0.96 (d)
1JPt,P ϭ 4211
0.69(d)
3JPt,PCH ϭ 45
4
4
3.57 (d, 2 H, PCH2)
3.52 (d, 2 H, PCH2)
2JP,CH or JP,CH
ϭ
ϭ
3.49 (d, 2 H, PCH2)
2JP,CH or JP,CH ϭ 3
1JPt,P ϭ 1648,
2JP,P ϭ 23
4, JPt,PCH ϭ 45
1JPt,P ϭ 1637,
2JP,P ϭ 21
3JPt,PCH ؍ 16
3
4
2JP,CH or JP,CH
2.45 (t, 2 H, CH2NCH2P)
3JCH,CH ϭ 7
3
4, JPt,PCH ؍ 15
2.57 (t, 2 H, CH2NCH2P)
0.33 (dd, 3 H, CH3)
3JCH,CH ϭ 6
3JP,CH ϭ 4,
3JPЈCH ϭ 7
2JPt,CH ϭ 54
1.71 (quint, 2 H, AdeCH2CH2) 3JCH,CH ϭ 7
0.32 (dd, 3 H, CH3)
3JP,CH ϭ 4,
3JPЈCH ϭ 7,
2JPtCH ϭ 54
8.25 (s, 1 H, C2-H)
7.76 (s, 1 H, C8-H)
7.71Ϫ7.41(m, 20 H, PhH)
5.63 (br. s, 2 H, NH2)
4.29 (d, 4 H, PCH2)
8.25 (s, 1 H, C2-H)
7.60 (s, 1 H, C8-H)
7.56Ϫ7.43 (m, 20 H, PhH)
5.76 (br. s, 2 H, NH2)
11a[b]
17.41 (s)
11b[b]
17.34 (s)
2JP,CH or
4JP,CH ϭ 1
3JCH,CH ϭ 7
4.29 (d, 4 H, PCH2)
2JP,CH or
4.01 (t, 2 H, AdeCH2CH2)
2.90 (t, 2 H, CH2NCH2P)
1.79 (quint, 2 H, AdeCH2CH2) 3JCH,CH ϭ 7
4JP,CH ϭ 1
3JCH,CH ϭ 6
3JCH,CH ϭ 6
3.94 (t, 2 H, AdeCH2CH2)
3.42 (t, 2 H, CH2NCH2P)
8.11 (s, 1 H, C2-H)
7.81Ϫ7.39 (m, 20 H, PhH ϩ C8-H)
5.47 (br. s, 2 H, NH2)
5.03 (d, 4 H, ArH of Cy)
4.94 (d, 4 H, ArH of Cy)
3.71 (br. s, 4 H, PCH2)
3.59 (t, 2 H, AdeCH2CH2)
2.37 [sept, 2 H, CH(CH3)2]
2.07 (t, 2 H, CH2NCH2P)
1.67 (s, 6 H, CH3)
3JCH,CH ϭ 7
3JCH,CH ϭ 6
3JCH,CH ϭ 6
12a[a]
20.10 (s)
3JCH,CH ϭ 6
3JCH,CH ϭ 6
3JCH,CH ϭ 6
0.85 [d, 12 H, CH(CH3)2]
3JCH,CH ϭ 6
Eur. J. Inorg. Chem. 2003, 2426Ϫ2437
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2433

Q. Zhang, G. Hua, P. Bhattacharyya, A. M. Z. Slawin, J. D. Woollins
FULL PAPER
Figure 2. (top) Molecular structure of complex 10b; (bottom) crystal structure of complex 10b showing part of the hydrogen bonding
N 43.72; found C 49.37, H 6.28, N 42.73. IR (KBr disc): ν˜ ϭ 3349
m cmϪ1, 3282s, 3112s, 1684vs, 1607vs. EIMS: m/z ϭ 192 [M]ϩ.
mixture was stirred at 0Ϫ5 °C for 2 h, dried over molecular sieves
and then passed through a short celite pad. The filtrate was concen-
trated to ca. 1 cm3 by rotary evaporation. Et2O (20 cm3) was then
added to precipitate the product, and filtration, washing with Et2O
(3 ϫ 1 cm3) and drying in vacuo gave a white solid. Yield: 222 mg,
92%. C33H32N6O2P2 (606.6): calcd. C 65.34, H 5.32, N 13.85; found
C 62.49, H 5.90, N 12.02. IR (KBr disc): ν˜ ϭ 3326m cmϪ1, 3179m,
1648vs, 1599s, 1178vs, 718vs, 696vs. FABMSϩ: m/z ϭ 629 [M ϩ
Na]ϩ, 607 [M ϩ H]ϩ.
9-(2-{Bis[(diphenylphosphanoyl)methyl]amino}ethyl)adenine (La): To
a solution of 9-(2-aminoethyl)adenine (1.150 g, 6.45 mmol) in
acetonitrile (150 cm3) was added Ph2PCH2OH (2.79 g,
12.90 mmol). The mixture was refluxed overnight and then concen-
trated in vacuo until the solution became opaque (ca. 20 cm3).
Cooling in a fridge overnight led to the precipitation of the prod-
uct. Subsequent filtration, and washing of the precipitate with cold
acetonitrile (3 ϫ 5 cm3) and cold Et2O (3 ϫ 30 cm3) gave the prod-
uct as a white solid. Yield: 2.14 g, 57.9%. C33H32N6P2 (574.6):
calcd. C 68.98, H 5.61, N 14.63; found C 67.54, H 5.47, N 13.90. IR
(KBr disc): ν˜ ϭ 3315m cmϪ1, 3136m, 1648vs, 1598vs, 742s, 696vs.
ESMSϩ: m/z ϭ 613 [M ϩ K]ϩ, 597 [M ϩ Na]ϩ, 575 [M ϩ H]ϩ.
9-(2-{Bis[(diphenylthiophosphanoyl)methyl]amino}ethyl)adenine
(5a): Elemental sulfur (35 mg, 1.06 mmol) was added to a solution
of La (300 mg, 522 µmol) in THF (20 cm3). The reaction mixture
was refluxed for 2 h and then concentrated to ca. 1 cm3 by rotary
evaporation. Et2O (20 cm3) was added to precipitate the product,
and filtration, washing with Et2O (3 ϫ 1 cm3) and drying in vacuo
gave a white solid. Yield: 300 mg, 88%. C33H32N6P2S2 (638.7):
calcd. C 62.05, H 5.05, N 13.16; found C 59.76, H 5.09, N 14.41.
9-(2-{Bis[(diphenylphosphanyl)methyl]amino}ethyl)adenine
(4a):
Aqueous hydrogen peroxide (92 µL, 811 µmol, 30%) was added to
a solution of La (231 mg, 402 µmol) in THF (40 cm3). The reaction
2434
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2003, 2426Ϫ2437

Aminomethylphosphine Derivatives of Adenine
FULL PAPER
1648vs, 1599vs, 1573m, 1176s, 718s, 695s. FABMSϩ: m/z ϭ 643 [M
˚
Table 6. Selected bond lengths (A) and angles (°) in compound 10b
ϩ Na]ϩ, 621 [M ϩ H]ϩ.
Pt(1)ϪCl(1A)
Pt(1)ϪP(14)
P(14)ϪC(14)
C(14)ϪN(13)
C(12)ϪN(13)
C(11)ϪC(10)
N(9)ϪC(4)
C(8)ϪN(7)
C(6)ϪN(6)
C(6)ϪC(5)
2.337(4)
2.286(2)
1.840(9)
Pt(1)ϪC(40A)
Pt(1)ϪP(15)
P(15)ϪC(15)]
2.017(5)
2.219(2)
1.830(9)
1.453(9)
1.511(11)
1.483(10)
1.356(10)
1.360(10)
1.370(11)
1.389(11)
1.315(10)
9-(3-{Bis[(diphenylthiophosphanoyl)methyl]amino}propyl)adenine
(5b): Elemental sulfur (22 mg, 688 µmol) was added to a solution
of Lb (200 mg, 340 µmol) in THF (20 cm3). The reaction mixture
was refluxed for 2 h and concentrated to ca. 1 cm3 by rotary evap-
oration. Et2O (20 cm3) was added to precipitate the product, and
filtration, washing with Et2O (3 ϫ 1 cm3) and drying in vacuo gave
a white solid. Yield: 191 mg, 86%. C34H34N6P2S2 (652.8): calcd. C
62.56, H 5.25, N 12.87; found C 60.77, H 4.71, N 13.70. IR (KBr
disc): ν˜ ϭ 3315m cmϪ1, 3173w, 1638vs, 1597vs, 705, 692s.
FABMSϩ: m/z ϭ 675 [M ϩ Na]ϩ, 653 [M ϩ H]ϩ.
1.470(10) C(15)ϪN(13)
1.468(10) C(11)ϪC(12)
1.496(11) C(10)ϪN(9)
1.376(10) N(9)ϪC(8)
1.317(10) N(7)ϪC(5)
1.333(11) N(1)ϪC(6)
1.431(12) C(5)ϪC(4)
1.310(10) N(3)ϪC(2)
1.363(10)
C(4)ϪN(3)
C(2)ϪN(1)
9-(3-{Bis[(diphenylselenophosphanoyl)methyl]amino}propyl)adenine
(6b): Elemental selenium (54 mg, 684 µmol) was added to a solu-
tion of ligand 2 (200 mg, 340 µmol) in THF (20 cm3). The reaction
mixture was refluxed for 2 h and passed through a short celite pad.
The filtrate was concentrated to ca. 1 cm3 by rotary evaporation.
Et2O (20 cm3) was added to precipitate the product, and filtration,
washing with Et2O (3 ϫ 1 cm3) and drying in vacuo gave a white
solid. Yield: 176 mg, 69%. C34H34N6P2Se2 (746.6): calcd. C 54.70,
H 4.59, N 11.26; found C 54.31, H 4.46, N 11.67. IR (KBr disc):
ν˜ ϭ 3312m cmϪ1, 3162m, 1638vs, 1597s, 746m, 691vs. FABMSϩ:
m/z ϭ 769 [M ϩ Na]ϩ, 747 [M ϩ H]ϩ.
C(40A)ϪPt(1)ϪP(15)
Cl(1A)ϪPt(1)ϪP(14)
Pt(1)ϪP(14)ϪC(14)
C(14)ϪN(13)ϪC(15) 110.1(7)
C(15)ϪP(15)ϪPt(1) 115.6(3)
N(13)ϪC(12)ϪC(11) 113.3(8)
C(4)ϪN(9)ϪC(8)
C(8)ϪN(7)ϪC(5)
N(7)ϪC(5)ϪC(4)
N(3)ϪC(4)ϪC(5)
N(3)ϪC(2)ϪN(1)
N(1)ϪC(6)ϪC(5)
86.9(8)
89.88(15)
116.6(3)
C(40A)ϪPt(1)ϪCl(1A)
88.0(8)
95.27(9)
112.0(6)
112.0(6)
113.3(8)
112.3(8)
114.3(9)]
103.7(8)
112.7(8)
117.2(8)
115.8(8)
P(14)ϪPt(1)ϪP(15)
P(14)ϪC(14)ϪN(13)
N(13)ϪC(15)ϪP(15)
N(13)ϪC(12)ϪC(11)
N(9)ϪC(10)ϪC(11)
N(9)ϪC(8)ϪN(7)
N(9)ϪC(4)ϪC(5)
C(4)ϪN(3)ϪC(2)
C(2)ϪN(1)ϪC(6)
C(6)ϪC(5)ϪC(4)
106.4(7)
102.6(8)
112.9(8)
127.5(8)
128.8(9)
117.9(8)
[PdCl2(La)] (7a): [PdCl2(cod)] (48 mg, 169 µmol) was added to a
solution of La (100 mg, 169 µmol) in CH2Cl2. The reaction mixture
was stirred at room temperature for 2 h and then concentrated to
ca. 0.5 cm3. Addition of Et2O (10 cm3), filtration and washing with
light petroleum ether (3 ϫ 1 cm3) and Et2O (3 ϫ 1 cm3) gave the
product as a yellow solid. Yield: 102 mg, 80%. C33H32Cl2N6P2Pd
(751.9): calcd. C 52.78, H 4.29, N 11.19; found C 54.71, H 5.00, N
9.81. IR (KBr disc): ν˜ ϭ 3387m cmϪ1, 3203w, 1637vs, 1594s, 740s,
691s. ESMSϩ: m/z ϭ 790 [M ϩ K]ϩ, 774 [M ϩ Na]ϩ, 715 [M Ϫ
HCl]ϩ, 697 [M Ϫ NH3 Ϫ HCl]ϩ, 679 [M Ϫ HCl Ϫ Cl]ϩ.
IR (KBr disc): ν˜ ϭ 3320m cmϪ1, 3170w, 1638vs, 1597s, 705s, 692s.
FABMSϩ: m/z ϭ 661 [M ϩ Na]ϩ, 639 [M ϩ H]ϩ.
9-(2-{Bis[(diphenylselenophosphanoyl)methyl]amino}ethyl)adenine
(6a): Elemental selenium (55 mg, 696 µmol) was added to a solu-
tion of La (200 mg, 340 µmol) in THF (20 cm3). The reaction mix-
ture was refluxed for 2 h. After cooling, the mixture was passed
through celite. The filtrate was concentrated to ca. 1 cm3 by rotary
evaporation. Et2O (20 cm3) was added to precipitate the product,
and filtration, washing with Et2O (3 ϫ 1 cm3) and drying in vacuo
gave a white solid. Yield: 190 mg, 74.5%. C33H32N6P2Se2 (732.5):
calcd. C 54.11, H 4.40, N 11.47; found C 53.87, H 3.82, N 12.50.
IR (KBr disc): ν˜ ϭ 3333m cmϪ1, 3188m, 1654vs, 1595vs, 746m,
690s. FABMSϩ: m/z ϭ 757 [M ϩ Na]ϩ, 735 [M ϩ H]ϩ.
[PdCl2(Lb)] (7b): [PdCl2(cod)] (69 mg, 242 µmol) was added to a
solution of Lb (143 mg, 243 µmol) in CH2Cl2 (10 cm3). A yellow
precipitate appeared immediately. The reaction mixture was stirred
at room temperature for 2 h and then concentrated to ca. 0.5 cm3.
Addition of Et2O (10 cm3), filtration and washing with light petro-
leum ether (3 ϫ 1 cm3) and Et2O (3 ϫ 1 cm3) gave the product as
a yellow solid. Yield: 177 mg, 95%. C34H34Cl2N6P2Pd (765.9):
calcd. C 53.32, H 4.47, N 10.97; found C 49.74, H 4.03, N 10.81.
IR (KBr disc): ν˜ ϭ 3314m cmϪ1, 3144m, 1637vs, 1603s, 737s, 670s,
305w, 291m. ESMSϩ: m/z ϭ 789 [M ϩ Na]ϩ, 767 [M ϩ H]ϩ, 729
[M Ϫ Cl]ϩ, 694 [M Ϫ HCl Ϫ Cl]ϩ.
9-(3-{Bis[(diphenylphosphanoyl)methyl]amino}propyl)adenine (Lb):
Ph2PCH2OH (3.566 g, 16.5 mmol) was added to a solution of 9-(2-
aminoethyl)adenine (1.46 g, 7.60 mmol) in acetonitrile (300 cm3).
The mixture was refluxed overnight and then concentrated in vacuo
to ca. 20 cm3 until a white solid precipitated. The solvent was then
pipetted off. The solid was washed with CH3CN (2 ϫ 20 cm3) and
Et2O (2 ϫ 50 cm3). Drying in vacuo gave the product as a white
solid. Yield: 3.25 g, 55%. C34H34N6P2 (588.6): calcd. C 69.38, H
5.82, N 14.28; found C 67.96, H 5.83, N 15.01. IR (KBr disc): ν˜ ϭ
3297m cmϪ1, 3134m, 1667vs, 1599vs, 743s, 697vs. ESMSϩ: m/z ϭ
611 [M ϩ Na]ϩ, 589 [M ϩ H]ϩ.
[PtCl2(La)] (8a): [PtCl2(cod)] (65 mg, 171 µmol) was added to a
solution of La (102 mg, 177 µmol) in CH2Cl2 (20 cm3). The reac-
tion mixture was stirred for 2 h and then concentrated to ca. 0.5
cm3. Addition of Et2O (10 cm3), filtration and washing with light
petroleum ether (3 ϫ 1 cm3) and Et2O (3 ϫ 1 cm3) gave the product
as a white solid. Yield: 156 mg, 91%. C33H32Cl2N6P2Pt (840.6):
calcd. C 47.15, H 3.84, N 10.00; found C 47.01, H 3.10, N 9.74.
IR (KBr disc): ν˜ ϭ 3386m cmϪ1, 3185w, 1637vs, 1596s, 741s, 692s,
313w, 286w. ESMSϩ: m/z ϭ 804 [M Ϫ HCl]ϩ.
9-(3-{Bis[(diphenylphosphanoyl)methyl]amino}propyl)adenine (4b):
Aqueous hydrogen peroxide (77 µL, 679 µmol, 30%) was added to
a solution of Lb (200 mg, 340 µmol) in THF (40 cm3). The reaction
mixture was stirred at 0Ϫ5 °C for 2 h, dried over molecular sieves [PtCl2(Lb)] (8b): [PtCl2(cod)] (78 mg, 208 µmol) was added to a
and then passed through a short celite pad. The filtrate was concen-
trated to ca. 1 cm3 by rotary evaporation. Et2O (20 cm3) was added
to precipitate the product, and filtration, washing with Et2O (3 ϫ
solution of Lb (124 mg, 211 µmol) in CH2Cl2 (20 cm3). A white
precipitate appeared immediately. The reaction mixture was stirred
for 2 h and then concentrated to ca. 0.5 cm3. Addition of Et2O (10
1 cm3) and drying in vacuo gave a white solid. Yield: 182 mg, 86%. cm3), filtration and washing with light petroleum ether (3 ϫ 1 cm3)
C34H34N6O2P2 (620.6): calcd. C 65.80, H 5.52, N 13.54; found C
and Et2O (3 ϫ 1 cm3) gave the product as a white solid. Yield:
166 mg, 93%. C34H34Cl2N6P2Pt (854.6): calcd. C 47.34, H 3.46, N
62.87, H 5.94, N 11.42. IR (KBr disc): ν˜ ϭ 3324m cmϪ1, 3180m,
Eur. J. Inorg. Chem. 2003, 2426Ϫ2437
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Q. Zhang, G. Hua, P. Bhattacharyya, A. M. Z. Slawin, J. D. Woollins
FULL PAPER
10.32; found C 47.78, H 4.01, N 9.83. IR (KBr disc): ν˜ ϭ 3338m
C 38.76, H 3.08, N 7.98. IR (KBr disc): ν˜ ϭ 3317m cmϪ1, 3161m,
cmϪ1, 3163m, 1632vs, 1601s, 740s, 691vs, 314w, 292m. FABMSϩ: 1638vs, 1595s, 744s, 691vs, 326s. FABMSϩ: m/z ϭ 1017 [M Ϫ Cl]ϩ,
m/z ϭ 819 [M Ϫ Cl]ϩ, 783 [M Ϫ 2Cl]ϩ.
982 [M Ϫ 2 Cl Ϫ H]ϩ.
[RuCl2(η6-p-CH3C6H4iPr)(La)]
(12a):
[RuCl(µ-Cl)(p-CH3-
[Pt(CH3)2(La)] (9a): [Pt(CH3)2(cod)] (56 mg, 168 µmol) was added
to a solution of La (100 mg, 174 µmol) in CH2Cl2 (10 cm3). The
reaction mixture was stirred for 2 h and then concentrated to ca.
0.5 cm3. Addition of Et2O (10 cm3), filtration and washing with
light petroleum ether (3 ϫ 1 cm3) and Et2O (3 ϫ 1 cm3) gave the
product as a white solid. Yield: 124 mg, 62%. C35H38N6P2Pt
(799.8): calcd. C 52.56, H 4.79, N 10.51; found C 51.64, H 4.24, N
10.19. IR (KBr disc): ν˜ ϭ 3323m cmϪ1, 3179w, 1638vs, 1594s,
737m, 696s. ESMSϩ: m/z ϭ 825 [M ϩ Na]ϩ, 800 [M]ϩ, 783 [M
Ϫ CH3]ϩ.
C6H4iPr)]2 (52 mg, 85 µmol) was added to a solution of La (50 mg,
87 µmol) in CH2Cl2 (20 cm3). The reaction mixture was stirred for
2 h and then concentrated to ca. 0.5 cm3. Addition of Et2O (10
cm3), filtration and washing with Et2O (3 ϫ 1 cm3) gave the prod-
uct as an orange solid. Yield: 85 mg, 83%. C53H60Cl4N6P2Ru2
(1187.0): calcd. C 53.63, H 5.09, N 7.08; found C 52.22, H 5.11, N
6.96. IR (KBr disc): ν˜ ϭ 3338m cmϪ1, 3187w, 3054m, 1631vs,
1595s, 1474s, 1437s, 746s, 696vs. FABMSϩ: m/z ϭ 1188 [M ϩ H]ϩ,
1212 [M ϩ Na]ϩ.
[Pt(CH3)2(Lb)] (9b): [Pt(CH3)2(cod)] (77 mg, 234 µmol) was added
to a solution of Lb (138 mg, 234 µmol) in CH2Cl2 (10 cm3). The
reaction mixture was stirred for 2 h and then concentrated to ca.
0.5 cm3. Addition of Et2O (10 cm3), filtration and washing with
light petroleum ether (3 ϫ 1 cm3) and Et2O (3 ϫ 1 cm3) gave the
product as a white solid. Yield: 154 mg, 82%. C36H40N6P2Pt
(813.8): calcd. C 53.13, H 4.95, N 10.33; found C 52.41, H 4.52, N
10.66. IR (KBr disc): ν˜ ϭ 3328m cmϪ1, 3163w, 1637vs, 1598s,
737m, 695vs. FABMSϩ: m/z ϭ 798 [M Ϫ CH3]ϩ, 783 [M Ϫ H
Ϫ 2CH3]ϩ.
Table 7. Details of the X-ray data collections and refinements for
compounds 2b and 10b
Compound
2b
10b·1/4C6H14
Empirical formula
Crystal colour, habit
C8H10N8
C36.50H40.50ClN6P2Pt
Colourless, block Colourless, block
Crystal dimensions/mm 0.1 ϫ 0.1 ϫ 0.1 0.1 ϫ 0.1 ϫ 0.01
Crystal system
Space group
Orthorhombic
Pbca
15.2288(17)
8.7153(10)
15.4248(16)
2047
Orthorhombic
Pbca
7.9955(9)
19.312(2)
46.857(5)
7235
˚
a/A
˚
[PtCl(CH3)(La)] (10a): [PtCl(CH3)(cod)] (90 mg, 254 µmol) was ad- b/A
˚
ded to a solution of La (147 mg, 254 µmol) in CH2Cl2 (20 cm3). A
c/A
3
˚
U/A
Z
white solid precipitated out gradually. The reaction mixture was
stirred for 2 h and then concentrated to ca. 0.5 cm3. Addition of
Et2O (10 cm3), filtration and washing with light petroleum ether (3
ϫ 1 cm3) and Et2O (3 ϫ 1 cm3) gave the product as an off-white
solid. Yield: 190 mg, 91%. C34H35ClN6P2Pt (820.2): calcd. C 49.79,
H 4.30, N 10.25; found C 51.18, H 4.13, N 9.86. IR (KBr disc):
ν˜ ϭ 3320w cmϪ1, 3163w, 1638vs, 1595s, 739s, 694vs. FABMSϩ:
m/z ϭ 804 [M Ϫ CH3]ϩ, 785 [M Ϫ Cl]ϩ.
8
8
M
218.24
1.416
0.100
855.73
1.571
4.076
Dc/g cmϪ3
µ/mmϪ1
F(000)
Measured reflections
912
9475
3412
29689
Independent reflections 1419(0.0876)
(Rint
Final R1, ωR2[I Ͼ 2σ(I)] 0.0456, 0.1036
5187(0.1341)
)
0.0409, 0.0664
[PtCl(CH3)(Lb)] (10b): [PtCl(CH3)(cod)] (70 mg, 230 µmol) was ad-
ded to a solution of Lb (117 mg, 230 µmol) in CH2Cl2 (10 cm3). A
white solid precipitated out gradually. The reaction mixture was
stirred for 2 h and then concentrated to ca. 0.5 cm3. Addition of
Et2O (10 cm3), filtration and washing with light petroleum ether (3
ϫ 1 cm3) and Et2O (3 ϫ 1 cm3) gave the product as an off-white
solid. Yield: 149 mg, 91%. C35H37ClN6P2Pt (834.2): calcd. C 50.39,
H 4.47, N 10.07; found C 49.70, H 4.01, N 10.44. IR (KBr disc):
ν˜ ϭ 3323m cmϪ1, 3158m, 1636vs, 1600s, 738s, 694vs, 296m.
FABMSϩ: m/z ϭ 798 [M Ϫ Cl]ϩ, 784 [M Ϫ Cl Ϫ CH3]ϩ.
X-ray Crystallography: Table 7 lists details of data collections and
refinements for 2b and 10b. Data were collected at room tempera-
ture using Mo-Kα radiation with a SMART system. Intensities were
corrected for Lorentz-polarisation and for absorption. The struc-
tures were solved by the heavy-atom method or by direct methods.
The positions of the hydrogen atoms were idealised. Refinements
were by full-matrix least-squares based on F2 using SHELXTL.[35]
In complex 10b, there is disorder of the chlorine and the methyl
atoms attached to the platinum atom. The diagram in Figure 2
shows the major (70%) occupancy. CCDC-200672 (2b) and
-200673 (10b) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge
CB2 1EZ, UK; Fax: (internat.) ϩ44-1223/336-033; E-mail:
deposit@ccdc.cam.ac.uk].
[(AuCl)2(La)] (11a): [AuCl(tht)] (80 mg, 250 µmol) was added to a
solution of La (74 mg, 129 µmol) in CH2Cl2 (10 cm3). The reaction
mixture was stirred for 2 h and a solid precipitated out after ca.
10 min. The resulting mixture was concentrated to ca. 0.5 cm3. Ad-
dition of Et2O (10 cm3), filtration and washing with Et2O (3 ϫ 1
cm3) gave the product as a white solid. Yield: 124 mg, 96%.
C33H32Au2Cl2N6P2 (1039.4): calcd. C 38.13, H 3.10, N 8.09; found
C 38.14, H 2.53, N 8.25. IR (KBr disc): ν˜ ϭ 3321m cmϪ1, 3181w,
1639vs, 1596vs, 744s, 692s, 329m. FABϩ: m/z ϭ 1003 [M Ϫ Cl]ϩ,
967 [M Ϫ 2Cl Ϫ H]ϩ.
Acknowledgments
[(AuCl)2(Lb)] (11b): [AuCl(tht)] (80 mg, 250 µmol) was added to a
solution of Lb (75 mg, 127 µmol) in CH2Cl2 (10 cm3). The reaction
mixture was stirred for 2 h and a solid precipitated out after ca.10 -
min. The resulting mixture was concentrated to ca. 0.5 cm3. Ad-
dition of Et2O (10 cm3), filtration and washing with Et2O (3 ϫ 1
cm3) gave the product as a white solid. Yield: 120 mg, 92%.
We wish to thank the JREI for equipment grants, Johnson Matthey
plc for the loan of precious metals and Dr. Andrew Houlton for his
inspiration of this work. Qingzhi Zhang is indebted to St Andrews
University for financial support. We are also grateful to Dr.
Stephen M. Aucott and Mrs. Joanna Wheatley in this lab for the
kind donation of [PtMe2(cod)], [PtMeCl(cod)] and [AuCl(tht)]
C34H34Au2Cl2N6P2 (1053.5): calcd. C 39.18, H 3.25, N 7.98; found (tht ϭ tetrahydrothiophene).
2436  2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjic.org
Eur. J. Inorg. Chem. 2003, 2426Ϫ2437

Aminomethylphosphine Derivatives of Adenine
FULL PAPER
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Eur. J. Inorg. Chem. 2003, 2426Ϫ2437
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