Ammonium phenylphosphonamidodiselenoates and phenylphosphonamidodi-selenoic diamides from the selenation of primary and secondary amines

Article abstract of DOI:10.1002/zaac.201100257

By reacting two equivalents of primary or secondary amines with 2,4-bis(phenyl)-1,3-diselenadiphosphetane-2,4-diselenide (Woollins' reagent) at room temperature a series of new ammonium phenylphosphonamidodiselenoates 1-7 have been obtained in good to excellent yields (70-99 %). The first metal complex of phenylphosphonamidodiselenoate, the complex of Cd₂L ₄ (L = [Se₂PPh(NCH(CH₃)₂] ^-) (8) has been prepared from the reaction of diisopropylamine N-isopropyl-P-phenylphosphonamidodiselenoate with Cd(CH₃COO) ₂ in dichloromethane. Upon heating to 130 °C the ammonium phenylphosphonamidodiselenoates lose hydrogen selenide leading to the corresponding phenylphosphonamidodiselenoic diamides 9-11 in almost quantitative yields. The same products 9-11 can also be prepared directly from the reaction of primary amines with Woollins' reagent in refluxing toluene. Three representative X-ray structures are described. Copyright

Full text of DOI:10.1002/zaac.201100257

ARTICLE
DOI: 10.1002/zaac.201100257
Ammonium Phenylphosphonamidodiselenoates and
Phenylphosphonamidodi-selenoic Diamides from the Selenation of Primary
and Secondary Amines
Guoxiong Hua,[a] Rebecca A. M. Randall,[a] Alexandra M. Z. Slawin,[a] and
J. Derek Woollins*[a]
In Memory of Professor Kurt Dehnicke, A Fine Scientist in the Best Tradition of German Chemistry
Keywords: Woollins’ reagent; Amines; Ammonium phenylphosphonamidodiselenoates; Phenylphosphonamidodiselenoic di-
amides; X-ray diffraction
Abstract. By reacting two equivalents of primary or secondary amines P-phenylphosphonamidodiselenoate with Cd(CH3COO)2 in dichloro-
with 2,4-bis(phenyl)-1,3-diselenadiphosphetane-2,4-diselenide (Wool-
lins’ reagent) at room temperature a series of new ammonium phenyl-
phosphonamidodiselenoates 1–7 have been obtained in good to excel-
lent yields (70–99%). The first metal complex of phenylphosphonami-
dodiselenoate, the complex of Cd2L4 (L = [Se2PPh(NCH(CH3)2]–) (8)
methane. Upon heating to 130 °C the ammonium phenylphosphonami-
dodiselenoates lose hydrogen selenide leading to the corresponding
phenylphosphonamidodiselenoic diamides 9–11 in almost quantitative
yields. The same products 9–11 can also be prepared directly from the
reaction of primary amines with Woollins’ reagent in refluxing toluene.
has been prepared from the reaction of diisopropylamine N-isopropyl- Three representative X-ray structures are described.
of Cd2L4 (L = [Se2PPh(NCH(CH3)2]–) and three representative
Introduction
related single-crystal X-ray structures. To the best of our
knowledge this is the first reported synthesis and characterisa-
tion of ammonium phenylphosphonamidodiselenoates and
phenylphosphonamidodiselenoic diamides and the representa-
tive coordination compound, providing a valuable addition to
the library of phosphodiselenoate compounds known.
Despite their toxic nature in general, selenium compounds
have now found applications in many areas such as organic
synthesis,[1] biochemistry,[2] xerography,[3] the synthesis of
conducting materials[4] and semiconductors,[5] and ligand syn-
thesis.[6] A wide range of selenation reagents can introduce
selenium into organic substrates by both nucleophilic and elec-
trophilic pathways, and the resulting selenium-containing
products can be further converted into useful targets that may
or may not retain the selenium atom.[7] 2,4-Bis(phenyl)-1,3-
Results and Discussion
The ammonium phenylphosphonamidodiselenoates 1–6
were synthesised by reaction of Woollins’ reagent with two
molar equivalents of primary or secondary amines (Scheme 1).
However, the reaction of Woollins’ reagent with two molar
equivalents of isoproplyamine gave a mixed ammonium phen-
ylphosphonamidodiselenoate 7 (Scheme 2). It was found that
isoproplyamine was not pure but mixed with some diisopro-
plyamine (ca. 5%), which was formed during the purification
process with CaH2 (Scheme 3).
Breaking the four-membered ring in Woollins’ reagent forms
the ammonium phenylphosphonamidodiselenoates 1–7 in 70–
99% yields as either off-white solids or pale yellow pastes,
which are soluble in polar and chlorinated solvents such as
alcohols, dichloromethane and chloroform but are insoluble in
less polar solvents such as ethers and hexane. Compounds 1–
7 are air stable for several weeks, after that obvious signs of
degradation occur including reddening of the powders due to
the expulsion of elemental selenium; this decomposition is ac-
companied by the evolution of foul smelling gas. The charac-
diselenadiphosphethane-2,4-diselenide
[{PhP(Se)(μ-Se)}2]
(Woollins’ reagent, WR, a selenium counterpart of Lawesson’s
reagent) has proved to be an efficient selenation reagent in
organic synthetic chemistry in part due to its relatively pleasant
chemical properties and ready preparation.[8] Reactions of
Woollins’ reagent with organic substrates display a wide spec-
trum ranging from simple oxygen-selenium exchange to the
formation of complex phosphorus-selenium heterocycles as
well as surprising phosphorus-selenium-free products.[9–17]
Herein, as part of our investigation into the reactivity of Wool-
lins’ reagent towards different organic substrates, we report the
synthesis of a series of novel ammonium phenylphosphonami-
dodiselenoates and phenylphosphonamidodiselenoic diamides
from the selenation of primary/secondary amines, the complex
* Prof. Dr. J. D. Woollins
E-Mail: jdw3@st-and.ac.uk
[a] EaStCHEM School of Chemistry
University of St Andrews
Fife, KY16 9ST, UK
1800
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Selenation of Primary and Secondary Amines
1
terisation of 1–7 is based on elemental analyses, H, 13C, 31P
and 77Se NMR spectroscopy, IR spectroscopy and mass spec-
trometry. The elemental analyses for all compounds were satis-
factory. The 31P NMR spectra of 1–7 showed sharp singlet
signals in the range of 42.0–70.0 ppm, flanked by a single pair
of selenium satellites with 31P–77Se coupling constants in the
range of 612–636 Hz, which are much smaller than the values
in sodium phosphonodiselenoate salts (667–675 Hz),[18] indi-
cating a P–Se bond order of approximately 1.5 as expected.
This was further substantiated by the 77Se NMR spectra which
exhibited doublets in the range of 31.6–62.8 ppm, with match-
ing 31P–77Se coupling constants.
Attempts to crystallise ammonium salts proved unsuccessful
apart from compound 7, which was obtained by diffusion of
the dichloromethane solution into hexane at room temperature.
The building block for compound 7 is shown in Figure 1 and
Table 1. The P–Se bond lengths [2.1545(9) and 2.1537(8) Å] Figure 1. Single crystal structure of compound 7 (Hydrogen atoms on
carbon atoms omitted for clarity). Selected bond lengths /Å and
are slightly shorter than those found in amine salts of bisdise-
angles /° (esds in parentheses): Se(1)–P(1) 2.1545(9), Se(2)–P(1)
lenophosphonic acid [2.1280(11)–2.1350(12) Å][19] and other
2.1537(8), P(1)–N(1) 1.665(2), P(1)–C(1) 1.830(2), N(1)–C(7)
symmetrical phosphenium salts [ca. 2.13 Å],[20] however, be-
1.474(4), N(2)–C(10) 1.507(3), N(2)–C(13) 1.504(4); Se(1)–P(1)–
ing still intermediate between single bond [ca. 2.38 Å] and
double bond [P=Se double bond length ca. 2.08 Å],[21] indicat-
ing significant delocalisation of the negative charge over the
Se–P–Se fragment. It should be noted that the two Se···N dis-
tances between the anion and cation are significantly different
[6.024(2) Å for N(2)···Se(1) and 3.424(2) Å for N(2)···Se(2)].
Se(2) 116.57(4), Se(1)–P(1)–N(1) 114.62(9), Se(1)–P(1)–C(1)
106.76(10), Se(2)–P(1)–N(1) 105.79(9), Se(2)–P(1)–C(1) 109.15(10),
N(1)–P(1)–C(1) 103.05(14), P(1)–N(1)–C(7) 121.39(19), C(10)–N(2)–
C(10) 118.0(2).
The preparation of the first metal complex of ammonium
phenylphosphonamidodiselenoate has been carried out. Cad-
mium acetate dihydrate was stirred with two equivalents of 7
in dichloromethane at room temperature to generate the com-
plex 8 (Scheme 4). The complex was obtained in high yield
(98%) as a white solid soluble in dichloromethane. The 31P
NMR spectrum of 8 displays a sharp singlet at δP = 35.7,
flanked by a single pair of selenium satellites with a 31P–77Se
coupling constant of 554 Hz. Meanwhile the 77Se NMR spec-
trum showed a doublet at δSe = 225.5 with a matching coupling
constant. The results show that upon complexation there is not
only a change in chemical shift (a decrease at δP from 42.0 to
35.7 and an increase at δSe from 70.7 to 225.5) but also a
significant decrease in the 31P–77Se coupling constant (a de-
Scheme 1. Synthesis of ammonium phenylphosphonamidodiselenoates
1–6.
Scheme 2. Synthesis of ammonium phenylphosphonamidodiselenoate 7.
1
Scheme 3. Formation of small amount of diisopropylamine (ca. 5% based on H NMR spectroscopic analysis) in isopropylamine purification
process.
Z. Anorg. Allg. Chem. 2011, 1800–1806
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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G. Hua, R. A. M. Randall, A. M. Z. Slawin, J. D. Woollins
ARTICLE
Table 1. Details of the X-ray data collections and refinements for com-
pounds 7, 8, and 11.
Compound
7
8
11
Formula
M
C15H29N2PSe2 C18H26N2P2Se4Cd C20H21N2PSe
426.30
760.61
399.33
Crystal system Monoclinic
Triclinic
P1
Triclinic
P1
¯
¯
Space group
a /Å
b /Å
c /Å
α /°
P21/c
11.060(3)
11.767(3)
15.528(4)
90
8.5190(14)
11.663(2)
13.167(2)
90.897(4)
95.811(4)
96.400(4)
1238.2(4)
2
5.687(10)
10.2583(18)
16.204(2)
107.730(9)
90.680(5)
97.955(4)
2209.4(7)
2
β /°
108.299(7)
90
945.81(7)
4
γ /°
V /A3
Z
μ /mm–1
Reflections
collected
Independent
reflections
Rint
1.476
14281
2.040
12299
1.489
9000
3863
5604
4047
0.079
0.0429;
0.1819
0.1036;
0.2383
0.0954
0.0594;
0.1065
Figure 2. Single crystal structure of the complex 8 (Hydrogen atoms
on carbon atoms omitted for clarity). Selected bond lengths /Å and
angles /° (esds in parentheses): Cd(1)–Se(1) 2.668(2), Cd(1)–Se(2)
3.255(2), Cd(1)–Se(3) 2.794(2), Cd(1)–Se(4) 2.624(2), Se(1)–P(1)
2.151(5), Se(2)–P(1) 2.204(4), Se(3)–P(2) 2.161(5), Se(4)–P(2)
2.192(4), P(1)–N(1) 1.597(16), P(2)–N(2) 1.641(15), Cd(1)–Se(2A)
2.639(2); Se(1)–Cd(1)–Se(2) 73.80(6), Se(1)–Cd(1)–Se(2A) 99.68(7),
Se(1)–Cd(1)–Se(3) 92.60(7), Se(1)–Cd(1)–Se(4) 136.40(8), Se(1)–
Cd(1)–P(2) 112.75(10), Se(2A)–Cd(1)–Se(3) 147.11(7), Se(2A)–
Cd(1)–Se(4) 87.80(6), Se(3)–Cd(1)–Se(4) 81.81(7), Cd(1)–Se(1)–P(1)
R1;
wR2 [I Ͼ 2σ(I)] 0.1137
crease from 615 to 554 Hz). A similar pattern was found in
the 1H and 13C NMR spectra of 8 as in the starting material 7.
The mass spectrometry found the 1/2 expected parent ion at
m/z = 761.
The single-crystal X-ray structure of 8 was determined (Fig- 95.33(14), Cd(1)–Se(4)–P(2) 83.93(14), Se(1)–P(1)–Se(2) 110.9(2),
Se(1)–P(1)–N(1) 106.6(5), Se(2)–P(1)–N(1) 117.4(5), Se(3)–P(2)–
ure 2 and Table 1). Although no literature example of structur-
Se(4) 109.3(2), Se(3)–P(2)–N(2) 110.5(6), Se(4)–P(2)–N(2) 114.1(5).
ally characterised cadmium complexes with such NP(Se)Se
containing ligands have been found, one example of cadmium
complex of a similar OP(Se)Se containing ligand19 and many with two equivalents of the corresponding primary amine in
examples of OP(S)S containing ligands have been documen- refluxing toluene (Scheme 6).
ted.[22] All examples exhibit a structural motif of an eight-
Compounds 9–11 are soluble in common chlorinated sol-
membered Cd2P2Se4 or Cd2P2S4 ring with two terminal biden- vents and air stable for several months as sticky oils or solid.
tate ligands each bound to one cadmium atom via both sele- Their formulations were confirmed by IR spectroscopy, MS
nium/sulfur atoms and the other two acting as bridging ligands (including accurate mass measurement), solution multinuclear
with their selenium/sulfur atoms binding to two different cad- NMR spectroscopy and one representative X-ray structure de-
mium atoms. Not surprisingly, the structure of compound 8 termination. The 31P NMR spectra of 9–11 showed sharp sing-
shows a dimeric complex in the solid state with an eight-mem- let signals at δP = 60.3, 46.0 and 62.4, respectively, the singlet
bered Cd2P2Se4 ring, flanked by two four-membered rings, in each case was flanked by a single pair of selenium satellites
which is very closely related to the similar OP(Se)Se com- with 31P–77Se coupling constants in the range of 763–813 Hz,
plex.[18,23,24]
indicating typical P=Se double bond character. This was fur-
Heating a toluene solution of ammonium phenylphosphona- ther confirmed by the 77Se NMR spectra which exhibited dou-
midodiselenoates to reflux for 12 h led to the corresponding blets at δSe = –243.2, –180.4 and –250.4, respectively with
1
phenylphosphonamidodiselenoic diamides 9–11 in almost matching 31P–77Se coupling constants. The H and 13C NMR
quantitative isolated yields with evolution of hydrogen sele- spectra of 9–11 were as expected confirming the presence of
nide (Scheme 5). The same products 9–11 could be also ob- phenyl and NH moieties. Mass spectra for them showed the
tained in 90–95% yields via the reaction of Woollins’ reagent expected parent ions as [M + Na].
Scheme 4. Synthesis of the complex 8.
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 1800–1806

Selenation of Primary and Secondary Amines
Scheme 5. Synthesis of phenylphosphonamidodiselenoic diamides 9–11 from ammonium phenylphosphonamidodiselenoates.
Scheme 6. Synthesis of phenylphosphonamidodiselenoic diamides 9–11 from the direct selenation of primary amines.
Compound 11 was crystallised by slow evaporation of [1.652(3) and 1.664(3) Å], compared to the other typical P–N
dichloromethane solution to give transparent, colourless cubic single bond system [ca. 1.80 Å],[25] suggesting the more or less
crystals. The data for X-ray structure of compound 11 is shown extent of resonance delocalisation.
in Figure 3 and Table 1 The phenyl rings attached to phospho-
rus atom via a CH2–NH bridge are opposite positions with an
Conclusions
inclined angle of 74.2° and being bent towards the different
side of the phenyl ring directly attached phosphorus atom with
angles of 61.8° and 76.5°, respectively. The single crystal
structure shows maginally longer P–Se double bond length
[2.1175(12) Å], compared to the normal double bond length
[ca. 2.08 Å][21] and significant shorter P–N single bond lengths
The reaction of Woollins’ reagent with the primary or sec-
ondary amines gives the non-symmetric phosphoronamidodi-
selenoate anions [Ph(R1R2N)PSe2]– as their ammonium salts
in good to excellent yields. The latter can be converted into
the corresponding phenylphosphonamido-diselenoic diamides
in almost quantitative yields with evolution of hydrogen sele-
nide. The same products, phenylphosphonamido-diselenoic di-
amides, can be directly obtained via the reaction of Woollins’
reagent with two equivalents of primary amine in excellent
yields. The first metal complex of a phosphoronamidodise-
lenoate anion shows a conformation with a dimeric nature,
which is very closely related to the known OP(Se)Se system.
Experimental Section
Unless otherwise stated, all reactions were carried out under on oxygen
free nitrogen atmosphere using pre-dried solvents and standard Schlenk
techniques, subsequent chromatographic and work up procedures were
1
performed in air. H (270 MHz), 13C (67.9 MHz), 31P{1H} (109 MHz)
and 77Se-{1H} (51.4 MHz referenced to external Me2Se) NMR spectra
were recorded at 25 °C (unless stated otherwise) with a JEOL GSX
270. IR spectra were recorded as KBr pellets in the range of 4000–
250 cm–1 with a Perkin–Elmer 2000 FTIR/Raman spectrometer. Micro-
analysis was performed by the University of St-Andrews microanalysis
service. Mass spectrometry was performed by the EPSRC National
Mass Spectrometry Service Centre, Swansea and the University of
St Andrews Mass Spectrometry Service. X-ray crystal data for 7,
were collected using the Rigaku STANDARD system[26] and for 8 and
11 using a Rigaku SCXMIni Mercury CCD system. Intensity data
were collected using ω steps accumulating area detector images
spanning at least a hemisphere of reciprocal space. All data were cor-
Figure 3. Single crystal structure of compound 11 (Hydrogen atoms
on carbon atoms omitted for clarity). Selected bond lengths /Å and
angles /° (esds in parentheses): Se(1)–P(1) 2.1175(12), P(1)–N(1)
1.652(3), P(1)–N(2) 1.664(3), P(1)–C(15) 1.811(5), N(1)–C(1)
1.475(6), N(2)–C(8) 1.449(5); Se(1)–P(1)–N(1) 116.50(12), Se(1)–
P(1)–N(2) 107.49(13), Se(1)–P(1)–C(15) 115.34(15), N(1)–P(10)–
N(2) 106.75(18), N(1)–P(1)–C(15) 102.21(20), N(2)–P(1)–C(15)
108.00(18), P(1)–N(1)–C(1) 118.2(3), P(1)–n(2)–C(8) 125.6(3).
Z. Anorg. Allg. Chem. 2011, 1800–1806
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G. Hua, R. A. M. Randall, A. M. Z. Slawin, J. D. Woollins
ARTICLE
rected for Lorentz polarisation effects. Absorption effects were cor- 129.1, 128.6, 128.3, 128.0, 127.8, 126.6, 126.4, 126.1, 47.5, 43.2 ppm.
rected on the basis of multiple equivalent reflections or by semi-empiri- 31P NMR ([D8]THF, δ), 46.1 (s, J(P,Se) = 634 Hz) ppm. 77Se NMR
cal methods. Structures were solved by direct methods and refined by ([D8]THF, δ), 39.9 (d, J(P,Se) = 634 Hz) ppm. Mass spectrum [ES–,
full-matrix least-squares against F2 by using the program m/z]: 374 [M
–
H2CH2Se]–. [ES+, m/z]: 108 [M–C6H5P(Se)
NHCH2C6H5Se]–. Accurate mass measurement (ES–MS): 373.9115,
SHELXTL.[27] Hydrogen atoms were assigned riding isotropic dis-
placement parameters and constrained to idealised geometries. CCDC- calculate mass for [C20H22N2PSe2–C6H5CH2NH2]: 373.9116.
829188 (7), -829187 (8), -829186 (11) contain the supplementary crys-
N-Benzyl-2-phenylethanamine
N-benzyl-N-phenethyl-P-phenyl-
tallographic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cam-
bridge Crystallographic Data centre, 12 Union Road, Cambridge CB2
1EZ, UK; Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk.
phosphonamidodiselenoate (4): A reddish golden paste (1.280 g,
93% yield). C34H38N2PSe2 (663.57): C, 61.54; H, 5.77; N, 4.22.
Found: C, 61.52; H, 5.95; N, 4.41. Selected IR (KBr): 1601(w),
1494(m), 1434(m), 1454(m), 1092(m), 747(s), 696(vs), 544(m),
1
486(m) cm–1. H NMR (CD2Cl2, δ), 8.38 (dd, J(P,H) = 13.8, J(H,H)
General Procedure for the Formation of Ammonium Phenylphos-
phonamidodiselenoates 1–7
= 7.2 Hz, 2 H, Ar–H), 8.02 (wide peak, 2 H, NH), 7.47–6.81 (m, 13
H, Ar–H), 4.12 (s, 4 H, CH2), 3.27–3.05 (m, 4 H, CH2), 2.65–2.51 (m,
4 H, CH2) ppm. 13C NMR (CD2Cl2, δ), 140.3, 137.1, 131.8, 131.6,
131.4, 130.0, 129.0, 128.8, 128.7, 128.6, 128.3, 128.2, 128.1, 127.9,
127.7, 127.5, 127.4, 126.9, 125.8, 51.7, 50.8, 47.5, 34.8, 32.7,
30.4 ppm. 31P NMR (CD2Cl2, δ), 70.0 (s, J(P,Se) = 620 Hz) ppm. 77Se
NMR (CD2Cl2, δ), 56.1 (d, J(P,Se) = 620 Hz) ppm. Mass spectrum
[ES–, m/z]: 454 [M – H2N(CH2C6H5)CH2CH2C6H5]–. Mass spectrum
[ES+, m/z]: 212 [H2N(CH2C6H5)CH2CH2C6H5]–.
A mixture of Woollins’ reagent (0.54 g, 1.0 mmol) and primary or sec-
ondary amine (4.0 mmol) in dry tetrahydrofuran (50 mL) was stirred
at room temperature. While the red suspension disappeared gradually
and a greyish white suspension formed after stirring at room tempera-
ture for 2 h. Upon evaporating to remove the solvent the residue was
dissolved in dichloromethane. After removal of insoluble solid with a
celite pad, the filtrate was dried in vacuo to give ammonium phenyl-
phosphonamidodiselenoates 1–7.
Diisobutylamine N,N-diisobutyl-P-phenylphosphonamidodiseleno-
ate (5): An orange paste (1.000 g, 95% yield). C22H42N2PSe2
(523.48): C, 50.48; H, 8.09; N, 5.35. Found: C, 50.69; H, 8.35; N, 5.70.
Selected IR (KBr): 1560(m), 1468(s), 1435(m), 1388(m), 1368(m),
1092(m), 988(m), 769(m), 748(m), 695(s), 554(s), 511(s) cm–1. 1H
NMR (CD2Cl2, δ), 8.24 (dd, J(P,H) = 13.9, J(H,H) = 7.2 Hz, 2 H, Ar–
H), 7.90 (wide peak, 2 H, NH), 7.30–7.28 (m, 3 H, Ar–H), 2.82 (dd,
J(H,H) = 7.2, J(H,H) = 7.7 Hz, 4 H, CH2), 2.80 (d, J(H,H) = 7.2 Hz,
4 H, CH2), 2.13 (septet, J(H,H) = 6.9 Hz, 2 H, CH), 1.81 (septet,
J(H,H) = 6.6 Hz, 2 H, CH), 1.01 (d, J(H,H) = 6.6 Hz, 6 H, CH3), 0.75
(d, J(H,H) = 6.6 Hz, 6 H, CH3) ppm. 13C NMR (CD2Cl2, δ), 142.8 (d,
J(P,C) = 83.0 Hz), 131.8 (d, J(P,C) = 11.4 Hz), 129.4 (d, J(P,C) =
3.1 Hz), 126.8 (d, J(P,C) = 12.5 Hz), 56.9, 53.8, 27.2 (d, J(P,C) =
7.3 Hz), 25.1, 20.6, 20.2 ppm. 31P NMR (CD2Cl2, δ), 63.9 (s, J(P,Se)
= 617 Hz) ppm. 77Se NMR (CD2Cl2, δ), 31.6 (d, J(P,Se) = 617 Hz)
ppm. Mass spectrum [ES–, m/z]: 396 [M – HN(C4H9)2]–, 129
[HN(C4H9)2]–.
Diethylamine N,N-diethyl-P-phenylphosphonamidodiselenoate (1):
A pale yellow paste (0.800 g, 97% yield). C14H42N2PSe2 (427.39): C,
39.34; H, 9.91; N, 6.55. Found: C, 39.70; H, 10.01; N, 6.70. Selected
IR (KBr): 1565(w), 1458(m), 1434(s), 1381(s), 1167(s), 1090(m),
1055(s), 1013(s), 905(m), 745(m), 691(s), 547(vs, P–Se), 500(s) cm–
1
1. H NMR (CD2Cl2, δ), 8.17–8.09 (m, 2 H, Ar–H), 7.33–7.32 (m, 3
H, Ar–H), 6.84 (wide peak, 2 H, NH), 3.20–3.08 (m, 4 H, CH2), 3.03–
2.95 (m, 4 H, CH2), 1.31 (t, J(H,H) = 7.2 Hz, 6 H, CH3), 1.02 (t,
J(H,H) = 6.9 Hz, 6 H, CH3) ppm. 13C NMR (CD2Cl2, δ), 130.9 (Ar–
C), 130.7 (Ar–C), 129.6 (Ar–C), 127.2 (d, J(P,C) = 12.5 Hz, (Ar–C)),
53.1 (CH2), 41.5 (CH2), 13.9 (CH3), 11.2 (CH3) ppm. 31P NMR
(CD2Cl2, δ), 55.8 (s, J(P,Se) = 615 Hz) ppm. 77Se NMR (CD2Cl2, δ),
62.8 (d, J(P,Se) = 616 Hz) ppm. Mass spectrum [ES–, m/z]: 348 [M –
HN(C2H5)2]–.
Butan-1-amine N-butyl-P-phenylphosphonamidodiselenoate (2): A
pale yellow condensed oil (0.810 g, 98% yield). C14H26N2PSe2
(411.26): C, 40.89; H, 6.37; N, 6.81. Found: C, 41.10; H, 6.55; N, 6.70.
Selected IR (KBr): 1640(w), 1582(m), 1479(m), 1435(m), 1387(m),
1096(m), 1069(m), 740(m), 690(m), 554(s, P–Se), 496(s) cm–1. 1H
NMR (CD2Cl2, δ), 8.12–8.06 (m, 2 H, Ar–H), 7.33–7.31 (m, 2 H, Ar–
H), 6.05 (wide peak, 3 H, NH3), 2.80 (t, J(H,H) = 6.9 Hz, 2 H, CH2),
2.66 (t, J(H,H) = 7.2 Hz, 2 H, CH2), 2.11 (wide peak, 1 H, NH), 1.57–
1.21 (m, 8 H, CH2), 0.92–0.79 (m, 6 H, CH3) ppm. 13C NMR (CD2Cl2,
δ), 130.4 (Ar–C), 130.3 (Ar–C), 129.8 (d, J(P,C) = 3.1 Hz, Ar–C),
127.5 (d, J(P,C) = 12.5 Hz, Ar–C), 43.4 (d, J(P,C) = 5.2 Hz), 40.2,
33.2 (d, J(P,C) = 9.3 Hz), 32.1, 20.2, 20.0, 13.7, 13.5 ppm. 31P NMR
(CD2Cl2, δ), 44.3 (s, J(P,Se) = 613 Hz) ppm. 77Se NMR (CD2Cl2, δ),
57.9 (d, J(P,Se) = 613 Hz) ppm. Mass spectrum [ES–, m/z]: 340 [M –
H2NC4H9]–.
Benzenamine N,P-diphenylphosphonamidodiselenoate (6): A yel-
low paste (0.640 g, 70% yield). C18H18N2PSe2 (451.24): C, 47.91; H,
4.02; N, 6.21. Found: C, 47.98; H, 4.25; N, 6.50. Selected IR (KBr):
1600(s), 1494(s), 1434(m), 1378(m), 1282(m), 1027(m), 905(s),
742(s), 689(s), 527(m), 478(m) cm–1. 1H NMR (Tetrahydrofuran-d8,
δ), 8.02–6.90 (m, 15 H, Ar–H), 6.71 (d, J(P,H) = 7.7 Hz, 1 H, NH),
5.39 (wide peak, 3 H, NH) ppm. 13C NMR (Tetrahydrofuran-d8, δ),
143.3 (d, J(P,C) = 87.2 Hz), 132.5 (d, J(P,C) = 3.1 Hz), 130.5, 126.8
(d, J(P,C) = 12.5 Hz), 129.5, 129.4, 129.2, 129.0, 128.8, 128.0, 127.8,
122.7, 119.6, 119.5, 119.0 ppm. 31P NMR (Tetrahydrofuran-d8, δ), 46.2
(s, J(P,Se) = 636 Hz) ppm. 77Se NMR (Tetrahydrofuran-d8, δ), 39.0
(d, J(P,Se) = 636 Hz) ppm. Mass spectrum [ES–, m/z]: 360 [M –
H2NC6H5]–, 93 [H2NC6H5]–.
Benzylamine N-benzyl-P-phenylphosphonamidodiselenoate (3): An Diisopropylamine N-isopropyl-P-phenylphosphonamidodiseleno-
off-white solid (0.902 g, 99% yield). M.p. 150–152 °C. C20H22N2PSe2 ate (7): A yellow solid (0.810 g, 95% yield). M.p. 119–120 °C.
(479.30): C, 50.11; H, 4.63; N, 5.85. Found: C, 50.20; H, 4.95; N, 6.01.
C15H29N2PSe2 (426.30): C, 42.26; H, 6.86; N, 6.57. Found: C, 42.40;
Selected IR (KBr): 1569(m), 1493(m), 1468(m), 1377(m), 1199(w), H, 7.05; N, 6.70. Selected IR (KBr): 1578(m), 1434(m), 1406(m),
1063(s), 732(m), 696(vs), 548(s), 483(s) cm–1. 1H NMR ([D8]THF, δ), 1129(m), 1093(m), 1023(m), 1020(m), 751(m), 694(m), 547(vs, P=Se),
1
8.28 (dd, J(P,H) = 13.8, J(H,H) = 7.9 Hz, 2 H, Ar–H), 7.55–7.07 (m,
500(m) cm–1. H NMR (CD2Cl2, δ), 8.15–8.08 (m, 2 H, Ar–H), 7.81
13 H, Ar–H), 6.72 (wide peak, 3 H, NH), 3.92 (d, J(P,H) = 9.3 Hz, 2 (wide peak, 2 H, NH), 7.32–7.27 (m, 3 H, Ar–H), 3.49–3.42 (m, 1 H,
H, CH2), 3.58 (s, 2 H, CH2), 3.40 (wide peak, 1 H, NH) ppm. 13C
NMR ([D8]THF, δ), 145.0, 143.9, 141.6, 141.4, 134.9, 130.9, 130.8,
CH), 3.32–3.22 (m, 1 H, CH), 2.48 (wide peak, 1 H, NH), 1.46 (d,
J(H,H) = 6.3 Hz, 12 H, CH3), 0.99 (d, J(H,H) = 6.6 Hz, 6 H, CH3)
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 1800–1806

Selenation of Primary and Secondary Amines
ppm. 13C NMR (CD2Cl2, δ), 130.5 (d, J(P,C) = 12.5 Hz, Ar–C), 129.4 (CD2Cl2, δ), 140.0 (d, J(P,C) = 3.1 Hz), 134.8 (d, J(P,C) = 113.1 Hz),
(Ar–C), 127.3 Ar–C), 127.1 (Ar–C), 48.6, 46.1, 24.8, 20.0 ppm. 31P 132.5 (d, J(P,C) = 3.1 Hz), 130.6 (d, J(P,C) = 11.4 Hz), 129.2, 129.1,
NMR (CD2Cl2, δ), 42.0 (s, J(P,Se) = 615 Hz) ppm. 77Se NMR 128.8, 122.7, 119.6, 119.5 ppm. 31P NMR (CD2Cl2, δ), 46.0 (s, J(P,Se)
(CD2Cl2, δ), 70.7 (d, J(P,Se) = 615 Hz) ppm. Mass spectrum [ES–, = 812 Hz) ppm. 77Se NMR (CD2Cl2, δ), –180.4 (d, J(P,Se) = 813 Hz)
m/z]: 326 [M – H2NC6H14]–.
ppm. Mass spectrum [ES+, m/z]: 395 [M + Na]+. Accurate mass mea-
surement (ES+MS): 395.0195, calculate mass for C18H17N2PSe
[M + Na]: 395.0192.
Bis(N-isopropyl-P-phenylphosphonamidodiselenoato)cadmium
(8):
N-isopropyl-P-phenylphosphonamidodiselenoate
(0.048 g,
0.1 mmol) and Cd(CH3COO)2•2H2O (0.013 g, 0.05 mmol) in dichlo-
romethane (10 mL) was stirred at room temperature for 2 h. A colour-
less solution formed. Upon filtering to remove unreacted solid, the
filtrate was dried in vacuo to give as a white solid (0.036 g) in 97%
yield. Colourless crystals suitable for X-ray analysis were grown by
N,N-Dibenzyl-P-phenylphosphinoselenoic amide (11): A yellow oil
(99% yield from Route A and 90% yield from Route B). Selected IR
(KBr): 1435(m), 1394(m), 1261(m), 1051(s), 800(s), 744(s), 695(vs),
1
550(m), 485(m) cm–1. H NMR (CD2Cl2, δ), 8.14–7.97 (m, 2 H, Ar–
H), 7.49–7.21(m, 13 H, Ar–H), 6.34 (wide peak, 2 H, NH), 4.16–4.06
(m, 4 H, CH2) ppm. 13C NMR (CD2Cl2, δ), 139.6, 135.9, 132.9, 132.0,
131.1, 131.0, 130.6, 130.5, 130.2, 129.2, 129.0, 128.6, 128.4, 127.6,
127.4, 127.2, 127.0, 45.9 ppm. 31P NMR (CD2Cl2, δ), 62.4 (s, J(P,Se)
= 775 Hz) ppm. 77Se NMR (CD2Cl2, δ), –250.4 (d, J(P,Se) = 775 Hz)
ppm. Mass spectrum [ES+, m/z]: 423 [M + Na]+. Accurate mass mea-
surement (ES+MS): 423.0507, calculate mass for C18H18N2PSeNa
[M + Na]: 423.0505.
vapour diffusion of hexane into
a dichloromethane solution.
C36H52N4P4Se8Cd2 (1521.22): C, 28.42; H, 3.45; N, 3.68. Found: C,
28.67; H, 3.70; N, 3.79. Selected IR (KBr): 1562(m), 1006(m), 880(s),
748(s), 692(s), 541(s) cm–1. 1H NMR (CD2Cl2, δ), 8.14–8.06 (m, 8 H,
Ar–H), 7.41–7.38 (m, 12 H, Ar–H), 3.25 (q, J(H,H) = 6.6 Hz, 4 H,
CH), 2.65 (very wide peak, 4 H, NH), 1.26 (d, J(H,H) = 6.6 Hz, 24
H, CH3) ppm. 13C NMR (CD2Cl2, δ), 138.8 (d, J(P,C) 83.0 Hz), 131.4
(d, J(P,C) = 3.1 Hz), 130.8 (d, J(P,C) = 13.5 Hz), 128.0 (d, J(P,C) =
13.5 Hz), 46.6, 19.3 ppm. 31P NMR (CD2Cl2, δ), 35.7 (s, J(P,Se) =
514 Hz) ppm. 77Se NMR (CD2Cl2, δ), 225.5 (d, J(P,Se) = 514 Hz)
ppm. Mass spectrum [MALDI, m/z]: 761 [1/2M]+, 440 [1/2M–
PSe2NC9H13]+.
Acknowledgments
The authors are thankful to the University of St Andrews and the Engi-
neering and Physical Science Research Council (EPSRC, U.K.) for
financial support.
General Procedure for Formation of Phenylphosphonamido-Diselenoic
Diamides 9–11
Route A: A toluene solution (20 mL) of ammonium phenylphosphona-
midodiselenoate (0.05 mmol) was heated to reflux under N2 gas for 12
h. Upon cooling to room temperature the mixture was evaporated to
remove solvent and the residue was purified by silica gel column
(dichloromethane as eluent) to afford the corresponding compounds 9–
11.
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Received: June 10, 2011
Published Online: August 25, 2011
1806
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 1800–1806