Sodium phenyldiselenophosphonate salts and Se-alkyl-O-alkylphenyl- phosphonodiselenoates and Se,Se??-dialkyl-O,O′-dialkyl- bis(phenylphosphonodiselenoate)s

Article abstract of DOI:10.1016/j.poly.2012.05.010

The reaction of sodium alkoxides [R¹ONa, R¹ = CH ₃, CH₃CH₂, (CH₃)₂CH and CH₃CH₂CH₂] with 2,4-diphenyl-1,3- diselenadiphosphetane-2,4-diselenide [PhP(Se)(μ-Se)]₂ (Woollins' reagent, WR) gave the non-symmetric sodium phenyldiselenophosphonate salts 1a-1d, the latter were further treated with haloalkanes [R²X, R ² = alkyl and aryl; X = Br, Cl and I] or dihaloalkanes [Br-(CH ₂)_n-Br, n = 1-3 and BrCH₂C₆H ₄CH₂Br-p] to afford a series of new Se-alkyl O-alkylphenylphosphonodiselenoate esters 2a-2k and Se,Se′-dialkyl-O, O′-dialkyl bis(phenylphosphonodiselenoate) esters 3a-3j in good to excellent yields.

Full text of DOI:10.1016/j.poly.2012.05.010

Polyhedron 42 (2012) 190–195
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Sodium phenyldiselenophosphonate salts and Se-alkyl-O-alkylphenyl-phosphono-
diselenoates and Se,Se0-dialkyl-O,O0-dialkyl-bis(phenylphosphonodiselenoate)s
⇑
Guoxiong Hua, J. Derek Woollins
EaStChem School of Chemistry, University of St. Andrews, Fife KY16 9ST, UK
a r t i c l e i n f o
a b s t r a c t
The reaction of sodium alkoxides [R1ONa, R1 = CH3, CH3CH2, (CH3)2CH and CH3CH2CH2] with 2,4-
diphenyl-1,3-diselenadiphosphetane-2,4-diselenide [PhP(Se)(l-Se)]2 (Woollins’ reagent, WR) gave the
non-symmetric sodium phenyldiselenophosphonate salts 1a–1d, the latter were further treated with
haloalkanes [R2X, R2 = alkyl and aryl; X = Br, Cl and I] or dihaloalkanes [Br-(CH2)n-Br, n = 1–3 and
BrCH2C6H4CH2Br-p] to afford a series of new Se-alkyl O-alkylphenylphosphonodiselenoate esters 2a–2k
and Se,Se0-dialkyl-O,O0-dialkyl bis(phenylphosphonodiselenoate) esters 3a–3j in good to excellent yields.
Crown Copyright Ó 2012 Published by Elsevier Ltd. All rights reserved.
Article history:
Received 29 March 2012
Accepted 14 May 2012
Available online 21 May 2012
Keywords:
Woollins’ reagent
Sodium phenyldiselenophosphonate salts
Se-Alkyl-O-
alkylphenylphosphonodiselenoate esters
Se,Se0-Dialkyl-O,O0-dialkyl
bis(phenylphosphonodiselenoate) esters
Mono-, di-haloalkanes
Phosphorus
Selenium
1. Introduction
[Ph(R1O)P(Se)SeR2, R1 = CH3, CH3CH2, (CH3)2CH and CH3CH2CH2, and
R2 = alkyl and aryl] and Se,Se0-dialkyl-O,O0-dimethyl bis(phenylphos-
The chemistry of selenium-containing diselenophosphates
phonodiselenoate) esters by the reaction of phenyldiselenophospho-
nate salts with haloalkanes or dihaloalkanes. All new compounds
have been characterized by IR, mass spectrometry and multinuclear
NMR. To the best of our knowledge this work is the first report of or-
ganic derivatives of phosphonodiselenoate salts and provides a valu-
able addition to the few examples of phosphonodiselenoate ligands
known.
[ðROÞ2PSeꢀ2 ], diselenophosphonate [ðRÞðROÞPSeꢀ2 ], diselenophosphi-
nates [R2PSeꢀ], and diselenophosphates [RPSe32ꢀ] with PSe2 or PSe3
2
functional groups has been less well studied compared to their sulfur
counterparts [1]. The coordination chemistry of diselenophosphi-
nates [R2PSeꢀ] and diselenophosphates [RPSe32ꢀ] was first described
2
in 1964 [2,3]. Since then, there have been a number of reports of the
synthesis and complexation of phosphinodiselenoate and phosp-
horodiselenoate ligands with a range of metals [4–8]. A varieties of
silver and copper containing cluster compound incorporating dial-
kylphosphorodiselenoate ligands have also been reported [9–15].
However, the reactivity ofthe diselenophosphates [(RO)2PSe2ꢀ], dise-
lenophosphonates [ðRÞðROÞPSeꢀ], diselenophosphinates [R2PSeꢀ],
2. Results and Discussion
Non-symmetric sodium phenyldiselenophosphonates [Ph(RO)
PSe2Na] 1a–1d were obtained via the cleavage of the four-mem-
bered P2Se2 ring in WR by two equivalents of sodium alkoxide
2
2
and diselenophosphates [RPSe32ꢀ] towards organic substrates re-
mains uninvestigated to date.
i
[NaOR (R = Me, Et, Pr and nPr)] at room temperature as either
white or pale yellow solids in high yields [30]. Then, sodium phen-
yldiselenophosphonates 1a–1c was stirred with one equivalent of
haloalkane in tetrahydrofuran at room temperature to yield the
corresponding Se-alkyl-O-alkylphenylphosphonodiselenoate esters
2a–2k as shown in Scheme 1. These new compounds were isolated
in high yields as sticky oils or pastes soluble in both chlorinated
solvents and tetrahydrofuran. Compounds 2a–2k are stable to air
and moisture for months without obvious signals of degradation.
It should be noted that 2i–2k bearing bulky R1 groups
(R1 = CH(CH3)2) were obtained in rather low yields, compared to
the compounds 2a–2k bearing small or medium R1 groups
2,4-Bis(phenyl)-1,3-diselenadiphosphetane-2,4-diselenide [PhP
(Se)(l-Se)]2, known as Woollins’ reagent, WR, is an efficient selena-
tion reagent in synthetic chemistry [16–28] due to its ready prepara-
tion and ease of handling in air [29]. Recently, we have reported the
synthesis of sodium phosphonodiselenoate salts achieved via a ring-
opening reaction of WR, and their metal complexes [30]. Herein, we
report a series of Se-alkyl O-alkylphenylphosphonodiselenoate esters
⇑
Corresponding author. Tel.: +44 1334 463384.
E-mail address: jdw3@st-and.ac.uk (J.D. Woollins).
0277-5387/$ - see front matter Crown Copyright Ó 2012 Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.05.010

G. Hua, J.D. Woollins / Polyhedron 42 (2012) 190–195
191
Se
Se
OR
OR
Se
BrEBr
THF, RT
Na/ROH
0 °C
P
P
P
P
P
E
Se
Se
SeNa
Se
1a - 1d
Se
Se
OR
Se
3a - 3l
WR
1a
1b
1c
1d
R = CH3
3a R = CH3, E = CH2CH2CH2, 94%
R = CH3CH2
R = (CH3)2CH
R = CH3CH2CH2
3b R = CH3, E = H2CC6H4CH2-p, 82%
3c R = CH3CH2, E = CH2, 72%
3d R = CH3CH2, E = CH2CH2, 78%
3e R = CH3CH2, E = CH2CH2CH2, 75%
3f
3g
3h
3i
R = CH3CH2, E = H2CC6H4CH2-p, 93%
R = (CH3)2CH, E = CH2CH2, 68%
R = (CH3)2CH, E = CH2CH2CH2, 66%
R = (CH3)2CH, E = H2CC6H4CH2-p, 58%
3j R = CH3CH2CH2, E = H2CC6H4CH2-p, 73%
Scheme 2. Synthesis of Se,Se0-dialkyl-O,O0-dialkyl-bis(phenylphosphonodiseleno-
ate) esters 3a–3j.
Scheme 1. Synthesis of Se-alkyl-O-alkylphenylphosphonodiselenoate esters 2a–2k.
(R1 = CH3 or CH2CH3), suggesting that steric hindrance of R1 groups
is important during the formation of the products. Use of haloalk-
anes with long chain alkyl groups also resulted in slightly lower
yields, for example, compound 2f is the lowest yield (with two
stereoisomers present).
small coupling constants 3J(P,Seendo) = 19.1 Hz and 4J(P,P)] = 4.8 Hz)
in 3c, 4J(P,Seendo) = 14.3 Hz in 3d and 3g, confirming the presence of
the corresponding P(Se)SeCH2SeP(Se) or P(Se)SeCH2CH2SeP(Se) motif
in compounds 3c, 3d and 3g. However, only one major compound was
observed for 3a, 3f, 3i and 3j, and no separate signals assignable to
either stereoisomeric forms were observed in their 1H, 13C, 31P and
77Se NMR spectra The 31P and 77Se chemical shifts and coupling con-
stants are comparable to the related heterocyclic compounds in the
literature [23,31–33].
Compounds 2a–2k showed the anticipated [M+H]+ or [M+Na]+
peaks in their mass spectra. The accurate mass measurements for
all of the compounds were satisfactory. The 31P NMR spectra of 2a–
2k reveal sharp singlets at d(P) in the range of 75.7–85.5 ppm, flanked
by two sets of selenium satellites with 31P–77Se coupling constants
in the range of 418–448 and 819–848 Hz (Table 1). The lower magni-
tude coupling constants are attributed to the P–Se single bonded
selenium atoms, and the higher magnitude values to the P@Se double
bonded selenium atoms. Meanwhile, the 77Se NMR spectra for 2a–2k
contain signals arising from exocyclic selenium atoms [d(Se) = ꢀ56.1
to ꢀ106.2 ppm; J(P,Seexo) = 819–848 Hz] and endocyclic selenium
atoms [d(Se) = 325.6–662.5 ppm; J(P,Seendo) = 418–448 Hz]. The 1H
and 13C NMR spectra confirm the presence of the organic substituents
on the phosphorus center. The multi-NMR spectra of 2f reveal a mix-
ture of two stereoisomers with similar 31P and 77Se NMR spectral pat-
Satisfactory accurate mass measurements were obtained for
3a–3j. The IR spectra display
m(P@Se) vibrations in the region of
492–551 cmꢀ1
.
In conclusion, a convenient and efficient approach to prepare a
series of novel Se-alkyl O-alkylphenylphosphonodiselenoate and
Se,Se0-dialkyl-O,O0-dialkyl bis(phenylphosphonodiselenoate) esters
has been developed from the reaction of haloalkane or dihaloal-
kane with sodium phenyldiselenophosphonates, which were de-
rived from a ring opening reaction of WR with the different
alkoxides. All of new compounds were fully characterized by IR,
mass spectroscopy and multinuclear NMR.
terns. In the IR spectra of 2a–2k the
m(P@Se) vibrations were
observed in the narrow region of 543–552 cmꢀ1
.
Similar reactions were carried out with dihaloalkanes instead of
haloalkanes. Thus the dihaloalkane was stirred with two equivalents
of sodium phenyldiselenophosphonates 1a–1d in tetrahydrofuran at
room temperature to give a series of new Se,Se0-dialkyl-O,O0-dialkyl-
bis(phenylphosphonodiselenoate) esters 3a–3j as shown in Scheme
2. These new compounds were isolated in high yields as sticky oils
or pastes soluble in chloroform, dichloromethane and tetrahydrofu-
ran, and insoluble in diethyl ether and hexane. The 31P NMR spectra
of 3b–3e, 3g and 3h exhibit two sets of double resonances (as a con-
sequence of the stereoisomers present) with two sets of satellites for
the endocyclic and exocyclic selenium atoms as shown in Table 2. De-
tailed 31P and 77Se NMR spectroscopic analyses reveal the relatively
3. Experimental
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 performed in air. 1H (270 MHz), 13C
(67.9 MHz), 31P–{1H} (109 MHz) and 77Se–{1H} (51.4 MHz refer-
enced to external Me2Se) NMR spectra were recorded at 25 °C
(unless stated otherwise) on a JEOL GSX 270. IR spectra were re-
corded as KBr pellets in the range of 4000–250 cmꢀ1 on a Perkin-
Elmer 2000 FTIR/Raman spectrometer. Mass spectrometry was
performed by the EPSRC National Mass Spectrometry Service
Table 1
31P and 77Se NMR data for compounds 2a–2k.
Product
d(P) [ppm]
J(P–Se)/J(P@Se) [Hz]
d(Seendo) [ppm]
J(Se–P) [Hz]
d(Seexo) [ppm]
J(Se = P) [Hz]
2a
2b
2c
2d
2e
2fa
84.3
84.3
84.5
75.7
84.8
85.5
85.1
80.0
80.1
77.3
77.1
77.6
446/826
448/848
427/833
423/840
451/826
420/832
434/837
444/824
444/822
439/819
441/822
418/826
386.3
399.7
327.1
662.5
325.6
369.6
332.6
411.8
399.4
421.5
431.9
361.0
446
448
427
424
453
420
434
444
446
439
439
417
ꢀ91.5
ꢀ95.7
ꢀ100.9
ꢀ56.1
ꢀ106.2
ꢀ98.6
ꢀ105.4
ꢀ88.9
ꢀ85.0
ꢀ82.6
ꢀ87.4
ꢀ90.2
827
848
834
839
825
832
837
825
823
819
823
827
2g
2h
2i
2j
2k
a
Two stereoisomers were found in 2f.

192
G. Hua, J.D. Woollins / Polyhedron 42 (2012) 190–195
Table 2
31P and 77Se NMR data for 3a–3j.
Product
d(P) [ppm]
J(P–Se)/J(P@Se) [Hz]
d(Seendo) [ppm]
J(Se–P) [Hz]
d(Seexo) [ppm]
J(Se = P) [Hz]
3a
3b
84.9
84.4
84.3
81.4
81.2
80.6
80.5
80.9
80.6
80.2
77.6
77.5
77.9
77.6
77.1
80.2
440/829
448/827
446/827
420/832
422/832
432/829
432/829
437/826
437/826
444/825
427/826
427/826
434/822
434/822
439/819
446/825
321.6
401.3
402.4
410.8
409.8
387.4
386.9
340.1
335.1
414.2
406.8
399.7
359.7
359.5
433.1
412.9
440
448
446
420
422
432
432
437
437
444
427
427
434
434
439
444
ꢀ108.8
ꢀ95.4
ꢀ94.2
ꢀ69.8
ꢀ97.1
ꢀ99.0
ꢀ99.2
ꢀ101.3
ꢀ101.6
ꢀ88.5
ꢀ94.2
ꢀ94.4
ꢀ96.5
ꢀ96.7
ꢀ87.1
ꢀ88.1
829
827
827
832
832
827
827
825
825
825
826
826
822
822
819
825
3c
3d
3e
3f
3g
3h
3i
3j
Centre, Swansea and the University of St. Andrews Mass Spectrom-
etry Service.
J(P,H) = 11.6 Hz, 2H, SeCH2), 4.17 (d, J(P,H) = 11.6 Hz, 2H, SeCH2),
3.76 (d, J(P,H) = 16.5 Hz, 3H, OCH3), 3.75 (d, J(P,H) = 16.5 Hz, 3H,
OCH3) ppm. 13C NMR (CD2Cl2, d), 193.8 (C = O), 135.4, 135.0, 133.7,
132.7, 132.6, 130.4 (d, J(P,C) = 12.5 Hz), 128.8, 128.6, 128.5, 128.3,
126.0, 53.2, 38.0 ppm. 31P NMR (CD2Cl2, d), 84.5 (s, J(P,Seendo) = 427 Hz,
3.1. General procedure for the synthesis of compounds 2a–2k
J(P,Seexo) = 833 Hz) ppm. 77Se NMR (CD2Cl2, d), 327.1 (d, J(P,Seendo
)
A
solution of haloalkane (2.0 mmol) and sodium phen-
= 427 Hz), ꢀ100.9 (d, J(P,Seexo) = 834 Hz) ppm. MS (CI+, m/z), 417
[M+H]+. Accurate mass measurement [CI+MS, m/z]: 416.9226
[M+H]+, calculated mass for C15H17O2PSe2: 416.9226.
yldiselenophosphonates (2.0 mmol) was stirred in dry tetrahydro-
furan (50 cm3) at room temperature under nitrogen gas for 20 h.
Upon filtering to remove insoluble solid, the filtrate was dried in
vacuum. The residue was purified by column chromatography (sil-
ica gel, eluent dichloromethane) to give the corresponding prod-
ucts 2a–2k.
3.1.4. Benzoic (O-methyl phenylphosphonoselenoic) selenoanhydride
(2d)
0.800 g as an yellow oil in 99% yield. Selected IR (KBr, cmꢀ1):
1735(m), 1687(s), 1580(w), 1438(s), 1196(s), 1172(s), 1105(m),
1024(s), 866(s), 686(s), 666(m), 543(s, P@Se). 1H NMR (CD2Cl2, d),
8.15–8.03 (m, 2H, ArH), 7.76 (d, J(H,H) = 7.2 Hz, 2H, ArH), 7.60
(m, 6H, ArH), 3.90, (d, J(P,H) = 16.8 Hz, 3H, OCH3) ppm. 13C NMR
(toluene-d8, d), 137.2, 133.8, 132.2, 132.1, 131.6, 131.4, 128.9,
128.6, 128.2, 128.0, 127.8, 127.7, 127.3, 125.2, 124.8, 124.5, 52.7
(d, 2J(P,C) = 6.2 Hz, OCH3) ppm. 31P NMR (toluene-d8, d), 75.7 (s,
J(P,Seendo) = 423 Hz, J(P,Seexo) = 840 Hz) ppm. 77Se NMR (toluene-
d8, d), 662.5 (d, J(P,Seendo) = 424 Hz), ꢀ56.1 (d, J(P,Seexo) = 839 Hz)
ppm. MS (CI+, m/z), 403 [M+H]+. Accurate mass measurement
[CI+MS, m/z]: 403.0039 [M+H]+, calculated mass for C18H20FePS2:
403.0037.
3.1.1. O-Methylphenyl-Se-2-bromobenzylphosphonodiselenoate (2a)
1.875 g as a colorless oil in 99% yield. Selected IR (KBr, cmꢀ1):
1472(m), 1437(s), 1105(s), 1023(vs), 779(m), 747(s), 713(m),
688(m), 548(vs P@Se), 499(s). 1H NMR (CD2Cl2, d), 7.96–7.88 (m,
2H, ArH), 7.52–7.50 (m, 3H, ArH), 7.23–7.04 (m, 4H, ArH), 4.07 (d,
J(P,H) = 11.6 Hz, 3H, OCH3), 3.68 (d, J(P,H) = 16.3 Hz, 2H, SeCH2)
ppm. 13C NMR (CD2Cl2, d), 133.0, 132.4 (d, J(P,C) = 3.1 Hz), 130.9,
130.5, 130.3, 129.1, 128.7, 128.5, 127.7, 124.7, 52.7, 36.5 ppm. 31P
NMR (CD2Cl2, d), 84.3 (s, J(P,Seendo) = 446 Hz, J(P,Seexo) = 826 Hz)
ppm. 77Se NMR (CD2Cl2, d), 386.3 (d, J(P,Seendo) = 446 Hz), ꢀ91.5
(d, J(P,Seexo) = 827 Hz) ppm. MS (CI+, m/z), 467 [M+H]+. Accurate
mass measurement [CI+MS, m/z]: 468.8377 [M+H]+, calculated
mass for C14H15BrOPSe2: 468.8378.
3.1.5. O-Methyl-Se-heptyl phenylphosphonodiselenoate (2e)
0.810 g as a colorless oil in 99% yield. Selected IR (KBr, cmꢀ1):
1437(m), 1106(m), 1024(vs), 777(m), 745(m), 714(m), 689(m),
552(vs P@Se), 502(m). 1H NMR (CD2Cl2, d), 7.96–7.88 (m, 2H,
ArH), 7.51–7.48 (m, 4H, ArH), 3.90 (d, (d, J(P,H) = 15.9 Hz, 3H,
OCH3), 1.96–1.54 (m, 5H, CH2), 1.27–1.22 (m, 9H, CH2), 0.86 (t,
J(H,H) = 6.3 Hz, 3H, CH3) ppm. 13C NMR (CD2Cl2, d), 132.3, 132.1,
130.2 (d, J(P,C) = 12.5 Hz), 128.4 (d, J(P,C) = 12.5 Hz), 14.4 Hz), 52.7
(OCH3), 32.9, 31.8, 30.5, 29.7, 28.5, 25.6, 22.7, 13.9 ppm. 31P NMR
(CD2Cl2, d), 84.8 (s, J(P,Seendo) = 451 Hz and J(P,Seexo) = 826 Hz)
ppm. 77Se NMR (CD2Cl2, d), 325.6 (d, J(P,Seendo) = 453 Hz), ꢀ106.2
(d, J(P,Seexo) = 825 Hz) ppm. MS (CI+, m/z), 411 [M+H]+. Accurate
mass measurement [CI+MS, m/z]: 411.0061 [M+H]+, calculated mass
for C15H26OPSe2: 411.0059.
3.1.2. O-Methylphenyl-Se-benzylphosphonodiselenoate (2b)
0.718 g as a colorless oil in 93% yield. Selected IR (KBr, cmꢀ1):
1493(m), 1437(m), 1179(m), 1022(vs), 779(m), 746(m), 691(s),
547(vs P@Se), 499(s). 1H NMR (CD2Cl2, d), 7.97–7.88 (m, 4H, ArH),
7.53–7.48 (m, 2H, ArH), 7.24–7.18 (m, 4H, ArH), 3.97 (d,
J(P,H) = 11.8 Hz, 3H, OCH3), 3.65 (d, J(P,H) = 16.3 Hz, 2H, SeCH2)
ppm. 13C NMR (CD2Cl2, d), 132.4 (d, J(P,C) = 3.1 Hz), 130.4, 130.3,
129.1, 128.7, 128.5, 127.3, 52.8, 36.1 ppm. 31P NMR (CD2Cl2, d),
84.3 (s, J(P,Seendo) = 448 Hz, J(P,Seexo) = 848 Hz) ppm. 77Se NMR
(CD2Cl2, d), 399.7 (d, J(P,Seendo) = 448 Hz), ꢀ95.7 (J(P,Seexo) = 848 Hz)
ppm. MS (CI+, m/z), 391 [M+H]+. Accurate mass measurement
[CI+MS, m/z]: 390.9267 [M+H]+, calculated mass for C14H16OPSe2:
390.9269.
3.1.3. O-Methyl-Se-2-oxo-2-phenylethyl phenylphosphonodiselenoate
(2c)
3.1.6. Ethyl 4-(methoxy(phenyl)phosphoroselenoylselanyl)-3-
oxobutanoate (2f)
0.741 g as a slightly yellow oil in 89% yield. Selected IR (KBr, cmꢀ1):
1595(m), 1579(m), 1438(m), 1272(s), 1180(s), 1106(m), 1020(s),
782(m), 746(s), 712(s), 687(s), 550(s, P@Se), 499(m). 1H NMR (CD2Cl2,
d), 7.99–7.85 (m, 4H, ArH), 7.58–7.42 (m, 6H, ArH), 4.18 (d,
0.640 g as a colorless oil in 75% yield. Selected IR (KBr, cmꢀ1):
1744(vs), 1630)(w), 1439(w), 1405(w), 1321(m), 1239(w), 1182(w),
1106(m), 1024(s), 783(m), 748(m), 714(m), 690(m), 551(vs), 501(m).
Two diasteroisomers in 10:1 ratio were found in multi-NMR spectra.

G. Hua, J.D. Woollins / Polyhedron 42 (2012) 190–195
193
1H NMR (CD2Cl2, d), 7.96–7.87 (m, 2H ꢁ 2, ArH), 7.59–7.44 (m, 3H ꢁ 2,
ArH), 4.27 (s, 2H ꢁ 2, CH2), 4.14 (q, J(H,H) = 7.2 Hz, 2H ꢁ 2, CH2), 3.76
(d, J(P,H) = 16.3 Hz, 3H, CH3O), 3.73 (d, J(P,H) = 16.3 Hz, 3H, CH3O),
3.60 (d, J(P,H) = 2.2 Hz, 2H, CH2), 3.51 (d, J(P,H) = 2.2 Hz, 2H, CH2),
1.24 (t, J(H,H) = 7.2 Hz, 3H ꢁ 2, CH3) ppm 13C NMR (CD2Cl2, d), 196.9,
195.2, 172.4 (d, J(P,C) = 15.6 Hz), 166.5 (d, J(P,C) = 16.6 Hz), 135.6 (d,
J(P,C) = 15.6 Hz), 132.8 (d, J(P,C) = 3.1 Hz), 132.6 (d, J(P,C) = 3.1 Hz),
130.4 (d, J(P,C) = 12.5 Hz), 128.7 (d, J(P,C) = 14.5 Hz), 128.6 (d,
J(P,C) = 14.5 Hz), 61.8, 61.6, 53.6, 53.3, 53.1, 53.0, 40.6 (d,
J(P,C) = 3.1 Hz), 40.2 (d, J(P,C) = 3.1 Hz), 14.1, 14.0 ppm. 31P NMR
(CD2Cl2, d), 85.5 (s, J(P,Seendo) = 420 Hz and J(P,Seexo) = 832 Hz); 85.1
(s, J(P,Seendo) = 434 Hz and J(P,Seexo) = 837 Hz) ppm. 77Se NMR (CD2Cl2,
d), 369.6 (d, J(P,Seendo) = 434 Hz), 332.6 (d, J(P,Seendo) = 434 Hz), ꢀ98.6
(J(P,Seexo) = 832 Hz), ꢀ105.4 (d, J(P,Seendo) = 437 Hz) ppm. Mass spec-
trum (ES+, m/z): 451 [M+Na]+. Accurate mass measurement [CI+MS,
m/z]: 426.9277 [M+H]+, calculated mass for C13H18O4PSe2: 426.9276.
7.88 (m, 2H, ArH), 7.50–7.32 (m, 4H, ArH), 7.20–7.18 (m, 4H,
ArH), 5.02–4.92 (m, 1H, CH), 4.11–3.93 (m, 2H, SeCH2), 1.36 (d,
J(H,H) = 6.3 Hz, 6H, CH3) ppm. 13C NMR (CD2Cl2, d), 138.1, 137.7,
132.1 (d, J(P,C) = 3.1 Hz), 130.3 (d, J(P,C) = 11.4 Hz), 129.1, 128.8,
128.6, 128.5, 127.3, 73.3 (d, J(P,C) = 7.3 Hz, O–C), 36.0, 35.9, 23.6
(d, J(P,C) = 35.3 Hz, Se–C), 23.5 (d, J(P,C) = 35.3 Hz, Se–C) ppm. 31P
NMR (CD2Cl2, d), 77.1 (s, J(P,Seendo) = 441 Hz and J(P,Seexo) =
822 Hz) ppm. 77Se NMR (CD2Cl2, d), 431.9 (d, J(P,Seendo) = 439 Hz),
ꢀ87.4 (d, J(P,Seexo) = 823 Hz) ppm MS (ES+, m/z), 441 [M+Na]+.
Accurate mass measurement (ES+MS): 440.9408 [M+Na]+, calculate
mass for [C16H19OPSe2Na]: 440.9403.
3.1.11. O-Isopropyl-Se-2-oxo-2-phenylethylphenylphosphonodiseleno
ate (2k)
0.372 g as a colorless oil in 83% yield. Selected IR (KBr, cmꢀ1):
1675(s), 1596(m), 1580(m), 1448(m), 1373(m), 1272(s), 1180(m),
1100(s), 962(vs), 746(s), 688(s), 549(s, P@Se), 496(m). 1H NMR
(CD2Cl2, d), 7.97–7.83 (m, 4H, ArH), 7.66–7.41 (m, 6H, ArH), 5.07–
4.93 (m, 1H, CH), 4.19 (d, J(P,H) = 10.7 Hz, SeCH2), 1.38 (dd,
J(P,H) = 10.2 Hz, J(H,H) = 6.3 Hz, 6H, CH3) ppm. 13C NMR (CD2Cl2,
d), 193.9(C = O), 134.0, 133.7, 132.5, 130.4 (d, J(P,C) = 12.5 Hz),
129.0, 128.8, 128.7, 128.4, 73.7 (d, J(P,C) = 7.3 Hz, O–C), 38.0 (CH3),
23.6 (d, J(P,C) = 29.1 Hz, Se–C) ppm. 31P NMR (CD2Cl2, d), 77.6 (s,
J(P,Seendo) = 418 Hz and J(P,Seexo) = 826 Hz) ppm. 77Se NMR (CD2Cl2,
d), 361.0 (d, J(P,Seendo) = 417 Hz), ꢀ90.2 (d, J(P,Seexo) = 827 Hz) ppm.
MS (ES+, m/z), 468 [M+Na]+. Accurate mass measurement (ES+MS):
467.9515 [M+Na]+, calculate mass for [C17H20NOPSe2Na]: 467.9511.
3.1.7. O-Ethyl-Se-benzylphenylphosphonodiselenoate (2g)
0.800 g as a red oil in 99% yield. Selected IR (KBr, cmꢀ1): 1437(m),
1104(m), 1020(s), 943(s), 745(m), 692(s), 545(s, P@Se), 497(m). 1H
NMR (CD2Cl2, d), 7.96–7.87 (m, 2H, ArH), 7.52–7.48 (m, 3H, ArH),
7.23–7.20 (m, 5H, ArH), 4.28–4.14 (m, 2H, OCH2), 4.01–3.95 (m,
2H, SeCH2), 1.33 (t, J(H,H) = 7.2 Hz, 3H, CH3) ppm. 13C NMR (CD2Cl2,
d), 132.3, 130.4, 130.3, 129.1, 128.7, 128.5, 128.2, 127.3, 63.1 (d,
J(P,C) = 6.2 Hz), 35.9, 15.5 (d, J(P,C) = 9.4 Hz) ppm. 31P NMR (CD2Cl2,
d), 80.0 (s, J(P,Seendo) = 444 Hz and J(P,Seexo) = 824 Hz) ppm. 77Se
NMR (CD2Cl2, d), 411.8 (d, J(P,Seendo) = 444 Hz), ꢀ88.9 (J
(P,Seexo) = 825 Hz) ppm. MS (CI+, m/z), 403 [M+H]+. Accurate mass
measurement [CI+MS, m/z]: 402.9434 [M+H]+, calculated mass for
3.2. General procedure for the synthesis of compounds 3a–3i
C15H18OPSe2: 402.9433.
A
mixture of dihaloalkane (1.0 mmol) and sodium phen-
3.1.8. O-Ethyl-Se-2-bromobenzylphenylphosphonodiselenoate (2h)
0.960 g as a slightly yellow oil in 99% yield. Selected IR (KBr,
cmꢀ1): 1438(m), 1104(m), 1023(vs), 943(s), 753(s), 713(m),
688(m), 548(vs P@Se), 496(m). 1H NMR (CD2Cl2, d), 7.97–7.88 (m,
2H, ArH), 7.52–7.44 (m, 3H, ArH), 7.21–7.04 (m, 4H, ArH), 4.31–
4.16 (m, 2H, OCH2), 4.12–3.95 (m, 2H, SeCH2), 1.35 (t,
J(H,H) = 7.2 Hz, 3H, CH3) ppm. 13C NMR (CD2Cl2, d), 132.9, 132.4
(d, J(P,C) = 3.1 Hz), 131.0, 130.5, 130.3, 129.1, 128.7, 128.5, 127.7,
63.2 (d, J(P,C) = 6.2 Hz), 36.4, 15.6 (d, J(P,C) = 9.4 Hz) ppm. 31P
NMR (CD2Cl2, d), 80.1 (s, J(P,Seendo) = 444 Hz and J(P,Seexo) = 822 Hz)
ppm. 77Se NMR (CD2Cl2, d), 399.4 (d, J(P,Seendo) = 446 Hz), ꢀ85.0
(d, J(P,Seexo) = 823 Hz) ppm. MS (CI+, m/z), 483 [M+H]+. Accurate
mass measurement [CI+MS, m/z]: 482.8518 [M+H]+, calculated
mass for C15H17BrOPSe2: 482.8523.
yldiselenophosphonates (2.0 mmol) in 50 cm3 of dry tetrahydrofu-
ran was stirred at room temperature under nitrogen gas for 20 h.
Upon filtering to remove insoluble solid, the filtrate was concen-
trated to approximate 5 cm3 in vacuum and purified by column
chromatography (silica gel, eluented by dichloromethane) to afford
the corresponding products 3a–3i.
3.2.1. O,O0-Dimethyl-Se,Se0-propane-1,3-diylbis(phenylphosphonodise
lenoate) (3a)
0.600 g as a colorless oil in 94% yield. Selected IR (KBr, cmꢀ1):
1435(s), 1291(w), 1238(s), 1106(m), 1022(vs), 778(m), 747(m),
713(m),689(m), 551(vs P@Se), 502(s, P@Se). 1H NMR (CD2Cl2, d),
7.96–7.87 (m, 4H, ArH), 7.56–7.45 (m, 6H, ArH), 3.75 (d,
J(P,H) = 16.3 Hz, 6H, OCH3), 3.55 (t, J(H,H) = 7.2 Hz, 4H, SeCH2),
2.37–2.30 (m, 2H, CH2) ppm. 13C NMR (CD2Cl2, d), 136.3 (d,
J(P,C) = 101 Hz), 132.5 (d, J(P,C) = 3.1 Hz), 130.3 (d, J(P,C) = 12.5 Hz),
128.6 (d, J(P,C) = 14.5 Hz), 52.9, 35.0, 32.9, 30.7 (d, J(P,C) = 3.1 Hz)
ppm. 31P NMR (CD2Cl2, d), 84.9 (s, J(P,Seendo) = 440 Hz,
J(P,Seexo) = 829 Hz) ppm. 77Se NMR (CD2Cl2, d), 321.6 (d,
J(P,Seendo) = 440 Hz), ꢀ108.8 (d, J(P,Seexo) = 829 Hz) ppm. MS (CI+,
m/z), 641 [M+H]+. Accurate mass measurement (CI+MS): 640.7833
[M+H]+, calculate mass for [C17H22O2P2Se4H]: 640.7838.
3.1.9. O-Isopropyl-Se-2-bromobenzylphenylphosphonodiselenoate
(2i)
0.415 g as a pale yellow oil in 84% yield. Selected IR (KBr, cmꢀ1):
1473(m), 1438(m), 1372(m), 1100(s), 1024(m), 962(vs), 753(s),
688(m), 547(vs P@Se), 495(m). 1H NMR (CD2Cl2, d), 7.94–7.85 (m,
2H, ArH), 7.52–7.47 (m, 4H, ArH), 7.15–7.04 (m, 3H, ArH), 5.03–
4.90 (m, 1H, CH), 4.20–4.01 (m, 2H, SeCH2), 1.36 (d, J(H,H) = 6.3 Hz,
6H, CH3) ppm. 13C NMR (CD2Cl2, d), 137.6, 132.9, 132.2, 131.0,
130.5, 130.3, 129.0, 128.6, 128.4, 127.6, 73.3 (d, J(P,C) = 6.2 Hz,
O–C), 36.5 (CH3), 23.5 (d, J(P,C) = 37.0 Hz, Se–C) ppm. 31P NMR
(CD2Cl2, d), 77.3 (s, J(P,Seendo) = 439 Hz and J(P,Seexo) = 819 Hz)
ppm. 77Se NMR (CD2Cl2, d), 421.5 (d, J(P,Seendo) = 439 Hz), ꢀ82.6
(d, J(P,Seexo) = 820 Hz) ppm. MS (ES+, m/z), 519 [M+Na]+. Accurate
mass measurement (ES+MS): 518.8509 [M+Na]+, calculate mass
for [C16H18BrOPSe2Na]: 518.8506.
3.2.2. O,O0-Dimethyl-Se,Se00-1,4-
phenylenebis(methylene)bis(phenylphosphonodiselenoate) (3b)
0.570 g as a colorless oil in 82% yield. Selected IR (KBr, cmꢀ1):
1509(m), 1477(m), 1435(s), 1178(s), 1105(s), 1020(vs), 778(s),
745(s), 712(m), 688(s), 548(vs P@Se), 498(s, P@Se). Two isomers
were found in ca. 10:1 intensity ratio in multi-NMR spectra. 1H
NMR (CD2Cl2, d), 7.92 (d, J(H,H) = 7.4 Hz, 4H ꢁ 2, ArH), 7.52–7.47
(m, 6H ꢁ 2, ArH), 7.07 (d, J(H,H) = 7.4 Hz, 4H ꢁ 2, ArH), 3.95 (d,
J(P,H) = 12.1 Hz, 4H, CH2), 3.93 (d, J(P,H) = 12.1 Hz, 4H, CH2), 3.65
(d, J(P,H) = 16.5 Hz, 6H, CH3), 3.64 (d, J(P,H) = 16.5 Hz, 6H, CH3)
ppm. 13C NMR (CD2Cl2, d), 137.0, 136.9, 135.5, 132.7 (d,
J(P,C) = 3.1 Hz), 132.5 (d, J(P,C) = 3.1 Hz), 130.3 (d, J(P,C) = 12.5 Hz),
3.1.10. O-Isopropyl-Se-benzylphenylphosphonodiselenoate (2j)
0.346 g as a colorless oil in 83% yield. Selected IR (KBr, cmꢀ1):
1494(m), 1453(m), 1437(m), 1372(m), 1178(m), 1100(s), 962(vs),
742(m), 692(s), 545(s, P@Se), 496(m). 1H NMR (CD2Cl2, d), 7.96–

194
G. Hua, J.D. Woollins / Polyhedron 42 (2012) 190–195
129.5, 129.4, 128.6 (d, J(P,C) = 14.5 Hz), 52.8, 52.7, 35.8, 35.7 ppm.
31P NMR (CD2Cl2, d), 84.4 (s, J(P,Seendo) = 448 Hz, J(P,Seexo) =
827 Hz), 84.3 (s, J(P,Seendo) = 446 Hz, J(P,Seexo) = 827 Hz) ppm.
77Se NMR (CD2Cl2, d), 402.4 (d, J(P,Seendo) = 446 Hz), 401.3 (d,
J(P,Seendo) = 448 Hz), ꢀ94.2 (d, J(P,Seexo) = 827 Hz), ꢀ95.4 (d,
J(P,Seexo) = 827 Hz) ppm. MS (ES+, m/z), 723 [M+Na]+. Accurate mass
measurement (ES+MS): 722.7803 [M+Na]+, calculate mass for
[C22H24O2P2Se4Na]: 722.7824.
3.2.6. O,O0-Diethyl-Se,Se0-1,4-
phenylenebis(methylene)bis(phenylphosphonodiselenoate) (3f)
0.560 g as a colorless oil in 77% yield. Selected IR (KBr, cmꢀ1):
1510(w), 1476(m), 1436(m), 1386(m), 1104(m), 1019(vs), 943(s),
744(s), 687(m), 548(vs P@Se), 496(s, P@Se). 1H NMR (CD2Cl2, d),
7.96–7.88 (m, 4H, ArH), 7.56–7.45 (m, 6H, ArH), 7.07 (d,
J(H,H) = 7.4 Hz, 4H, ArH), 4.28–4.11 (m, 4H, OCH2), 4.12–3.92 (m,
4H, SeCH2), 1.34 (t, J(H,H) = 6.9 Hz, 6H, CH3) ppm. 13C NMR (CD2Cl2,
d), 136.9 (d, J(P,C) = 4.2 Hz), 136.6 (d, J(P,C) = 100.7 Hz), 132.4 (d,
J(P,C) = 3.1 Hz), 130.4 (d, J(P,C) = 12.5 Hz), 129.4, 128.6 (d,
J(P,C) = 14.5 Hz), 63.1 (d, J(P,C) = 6.2 Hz, O–C), 35.6 (d,
J(P,C) = 4.2 Hz, Se–C), 15.9 ppm. 31P NMR (CD2Cl2, d), 80.2 (s,
J(P,Seendo) = 444 Hz, J(P,Seexo) = 825 Hz) pm. 77Se NMR (CD2Cl2, d),
414.2 (d, J(P,Seendo) = 444 Hz), ꢀ88.5 (d, J(P,Seexo) = 825 Hz) ppm.
MS (ES+, m/z), 753 [M+Na]+. Accurate mass measurement (ES+MS):
752.8114 [M+Na]+, calculate mass for [C24H28O2P2Se4Na]:
752.8123.
3.2.3. O,O0-Diethyl-Se,Se0-methylenebis(phenylphosphonodiselenoate)
(3c)
0.460 g as a colorless oil in 72% yield. Selected IR (KBr, cmꢀ1):
1474(m), 1436(s), 1385(m), 1104(s), 1027(vs), 943(s), 744(s), 687(s),
546(vs P@Se), 492(s, P@Se). Two isomers were found in ca. 1:1 inten-
sity ratio in multi-NMR spectra. 1H NMR (CD2Cl2, d), 7.92–7.88 (m,
4H ꢁ 2, ArH), 7.51–7.750 (m, 6H ꢁ 2, ArH), 4.274.23 (m, 2H ꢁ 2,
CH2), 4.14–3.92 (m, 4H ꢁ 2, CH2), 1.41 (t, J(H,H) = 6.9 Hz, 6H ꢁ 2,
CH3) ppm. 13C NMR (CD2Cl2, d), 136.1 (d, J(P,C) = 100 Hz), 132.6,
130.3 (d, J(P,C) = 12.5 Hz), 128.8, 128.5, 63.5, 63.4, 28.7, 28.5, 27.6,
27.5, 15.7, 15.5 ppm. 31P NMR (CD2Cl2, d), 81.4 (s, J(P,Seendo) = 420 Hz,
J(P,Seexo) = 832 Hz), 81.2 (s, J(P,Seendo) = 422 Hz, J(P,Seexo) = 832 Hz)
ppm. 77Se NMR (CD2Cl2, d), 410.8 (d, J(P,Seendo) = 420 Hz), 409.8 (d,
3.2.7. O,O0-Diisopropyl-Se,Se0-ethane-1,2-
diylbis(phenylphosphonodiselenoate) (3g)
0.460 g as a pale yellow oil in 68% yield. Selected IR (KBr, cmꢀ1):
1436(m), 1372(m), 1174(m), 1099(s), 962(vs), 885(m), 741(m),
688(m), 547(vs P@Se), 495(s, P@Se). Two isomers were found in
ca. 3:2 intensity ratio in multi-NMR spectra. 1H NMR (CD2Cl2, d),
7.90–7.88 (m, 4H, ArH), 7.60–7.48 (m, 6H, ArH), 4.96–4.93 (m,
2H, OCH), 3.01–2.98 (m, 4H, SeCH2), 1.50–1.31 (m, 12H, CH3)
ppm. 13C NMR (CD2Cl2, d), 137.5 (d, J(P,C) = (d, J(P,C) = 100.7 Hz),
132.3 (d, J(P,C) = 3.1 Hz), 130.2 (d, J(P,C) = 12.5 Hz), 128.5 (d,
J(P,C) = 14.5 Hz), 73.3 (d, J(P,C) = 6.2 Hz, O–C), 31.9, 30.5, 23.7 (d,
J(P,C) = 18.7 Hz), 23.6 (d, J(P,C) = 18.7 Hz) ppm. 31P NMR (CD2Cl2,
d), 77.6 (s, J(P,Seendo) = 427 Hz, J(P,Seexo) = 826 Hz), 77.5 (s,
J(P,Seendo) = 427 Hz, J(P,Seexo) = 826 Hz) pm. 77Se NMR (CD2Cl2, d),
406.8 (d, J(P,Seendo) = 427 Hz), 399.7 (d, J(P,Seendo) = 427 Hz),
ꢀ94.2 (d, J(P,Seexo) = 826 Hz), ꢀ94.4 (d, J(P,Seexo) = 826 Hz) ppm.
MS (CI+, m/z), 681 [M+H]+. Accurate mass measurement (CI+MS):
680.8313 [M+H]+, calculate mass for [C20H28O2P2Se4H]: 680.8317.
J(P,Seendo) = 422 Hz), ꢀ69.8 (d, J(P,Seexo) = 832 Hz), ꢀ97.1 (d,
J
(P,Seexo) = 832 Hz) ppm. MS (CI+, m/z), 641 [M+H]+. Accurate mass
measurement (CI+MS): 640.7831 [M+H]+, calculate mass for [C17H23O2
P2Se4]: 640.7838.
3.2.4. O,O0-Diethyl-Se,Se0-ethane-1,2-diylbis(phenylphosphonodisele
noate) (3d)
0.610 g as an yellow oil in 93% yield. Selected IR (KBr, cmꢀ1):
1436(s), 1385(m), 1162(m), 1103(s), 1018(vs), 943(s), 745(s),
689(s), 547(vs P@Se), 496(s, P@Se). Two isomers were found in ca.
3:2 intensity ratio in multi-NMR spectra. 1H NMR (CD2Cl2, d), 7.82–
7.74 (m, 4H ꢁ 2, ArH), 7.60–7.32 (m, 6H ꢁ 2, ArH), 4.16–3.92 (m,
4H ꢁ 2, OCH2), 3.01–2.88 (m, 4H ꢁ 2, SeCH2), 1.43–1.18 (m, 6H ꢁ 2,
CH3) ppm. 13C NMR (CD2Cl2, d), 136.8 (d, J(P,C) = 99.7 Hz), 132.4 (d,
J(P,C) = 3.1 Hz), 130.3 (d, J(P,C) = 12.5 Hz), 128.5 (d, J(P,C) = 14.5 Hz),
63.2 (d, J(P,C) = 6.2 Hz), 32.0, 15.7, 15.6 ppm. 31P NMR (CD2Cl2, d),
80.6 (s, J(P,Seendo) = 432 Hz, J(P,Seexo) = 829 Hz), 80.5 (s,
J(P,Seendo) = 432 Hz, J(P,Seexo) = 829 Hz) ppm. 77Se NMR (CD2Cl2, d),
387.4 (d, J(P,Seendo) = 432 Hz), 386.9 (d, J(P,Seendo) = 432 Hz), ꢀ99.0
(d, J(P,Seexo) = 827 Hz), ꢀ99.2 (d, J(P,Seexo) = 827 Hz) ppm. MS (ES+,
m/z), 677 [M+Na]+. Accurate mass measurement (ES+MS): 676.7804
[M+Na]+, calculate mass for [C18H24O2P2Se4Na]: 676.7810.
3.2.8. O,O0-Diisopropyl-Se,Se0-propane-1,3-diylbis(phenylphosphono
diselenoate) (3h)
0.455 g as a reddish yellow oil in 66% isolated yield. Selected IR
(KBr, cmꢀ1): 1436(m), 1371(m), 1100(s), 961(vs), 885(m), 741(s),
689(m), 548(vs P@Se), 496(s, P@Se). Two isomers were found in ca.
6:1 intensity ratio in multi-NMR spectra. 1H NMR (CD2Cl2, d), 7.95–
7.87 (m, 4H, ArH), 7.50–7.44 (m, 6H, ArH), 7.05 (d, J(H,H) = 7.4 Hz,
4H, ArH), 4.19–3.80 (m, 8H, OCH2+SeCH2), 1.76–1.65 (m, 4H, CH2),
1.00–0.94 (m, 6H, CH3) ppm. 13C NMR (CD2Cl2, d), 137.6 (d,
J(P,C) = 99.7 Hz), 137.5 (d, J(P,C) = 99.7 Hz), 132.2 (d, J(P,C) = 3.1 Hz),
130.2 (d, J(P,C) = 12.5 Hz), 128.4 (d, J(P,C) = 14.5 Hz), 73.1 (d,
J(P,C) = 6.2 Hz, O–C), 32.9 (d, J(P,C) = 3.1 Hz, Se–C), 31.9(d,
J(P,C) = 3.1 Hz, Se–C), 30.8, 30.5, 23.7 (d, J(P,C) = 19.7 Hz, CH3), 23.6
(d, J(P,C) = 20.8 Hz, CH3) ppm. 31P NMR (CD2Cl2, d), 77.9 (s,
J(P,Seendo) = 434 Hz, J(P,Seexo) = 822 Hz), 77.6 (s, J(P,Seendo) = 434 Hz,
J(P,Seexo) = 822 Hz) pm. 77Se NMR (CD2Cl2, d), 359.8 (d,
J(P,Seendo) = 434 Hz), 359.5 (d, J(P,Seendo) = 434 Hz), ꢀ96.5 (d,
J(P,Seexo) = 822 Hz), ꢀ96.7 (d, J(P,Seexo) = 822 Hz) ppm. MS (CI+, m/z),
695 [M+H]+. Accurate mass measurement (CI+MS): 694.8473
[M+H]+, calculate mass for [C21H30O2P2Se4H]: 694.8474.
3.2.5. O,O0-Diethyl-Se,Se0-propane-1,3-diyl bis(phenylphosphonodisele
noate) (3e)
0.490 g as an yellow oil in 75% yield. Selected IR (KBr, cmꢀ1):
1476(m), 1436(s), 1386(m), 1104(s), 1020(s), 942(s), 745(s),
712(m), 689(s), 549(vs P@Se), 497(s, P@Se). Two isomers were found
in ca. 8:1 intensity ratio in multi-NMR spectra. 1H NMR (CD2Cl2, d),
7.98–7.85 (m, 4H ꢁ 2, ArH), 7.53–7.45 (m, 6H ꢁ 2, ArH), 4.28–4.10
(m, 4H ꢁ 2, OCH2), 2.96–2.70 (m, 4H ꢁ 2, SeCH2), 2.13–1.88 (m,
2H ꢁ 2, CH2), 1.42–1.27 (m, 6H ꢁ 2, CH3) ppm. 13C NMR (CD2Cl2, d),
136.8 (d, J(P,C) = 99.7 Hz), 132.3 (d, J(P,C) = 3.1 Hz), 130.3 (d,
J(P,C) = 11.4 Hz), 128.5 (d, J(P,C) = 14.5 Hz), 63.1, 63.0, 32.0 (d,
J(P,C) = 3.1 Hz), 30.5 (d, J(P,C) = 3.1 Hz), 22.7, 22.6, 15.7, 15.6 ppm.
31P NMR (CD2Cl2, d), 80.9 (s, J(P,Seendo) = 437 Hz, J(P,Seexo) = 826 Hz),
80.6 (s, J(P,Seendo) = 437 Hz, J(P,Seexo) = 826 Hz) ppm. 77Se NMR
3.2.9. O,O0-Diisopropyl-Se,Se0-1,4-phenylenebis(methylene) bis(phenyl
phosphonodiselenoate) (3i)
0.435 g as a bright yellow oil in 58% isolated yield. Selected IR
(KBr, cmꢀ1): 1509(w), 1435(m), 1371(m), 1099(s), 961(vs),
885(m), 740(m), 688(m), 547(vs P@Se), 495(s, P@Se). 1H NMR
(CD2Cl2, d), 7.89–7.82 (m, 4H, ArH), 7.50–7.47 (m, 6H, ArH), 7.02
(d, J(H,H) = 7.4 Hz, 4H, ArH), 4.94–4.80 (m, 2H, OCH), 4.13–3.80
(m, 4H, SeCH2), 1.54–0.88 (m, 12H, CH3) ppm. 13C NMR (CD2Cl2,
(CD2Cl2,
d),
340.1
(d,
J(P,Seendo) = 437 Hz),
335.1
(d,
J(P,Seendo) = 437 Hz), ꢀ101.3 (d, J(P,Seexo) = 825 Hz), ꢀ101.6 (d,
J(P,Seexo) = 825 Hz) ppm. MS (ES+, m/z), 691 [M+Na]+. Accurate mass
measurement (ES+MS): 690.7960 [M+Na]+, calculate mass for
[C19H26O2P2Se4Na]: 690.7967.

G. Hua, J.D. Woollins / Polyhedron 42 (2012) 190–195
195
d), 137.2 (d, J(P,C) = 99.7 Hz), 136.8 (d, J(P,C) = 4.1 Hz), 132.2 (d,
References
J(P,C) = 3.1 Hz), 130.3 (d, J(P,C) = 12.5 Hz), 129.3, 128.5 (d,
J(P,C) = 14.5 Hz), 73.2 (d, J(P,C) = 6.2 Hz, O–C), 35.6, 23.7 (d,
J(P,C) = 33.2 Hz, CH3), 23.6 (d, J(P,C) = 33.3 Hz, CH3) ppm. 31P
NMR (CD2Cl2, d), 77.1 (s, J(P,Seendo) = 439 Hz, J(P,Seexo) = 819 Hz)
pm. 77Se NMR (CD2Cl2, d), 433.1 (d, J(P,Seendo) = 439 Hz), ꢀ87.1
(d, J(P,Seexo) = 819 Hz) ppm. MS (CI+, m/z), 774 [M+NH4]+. Accurate
mass measurement (CI+MS): 773.8894 [M+NH4]+, calculate mass
for [C26H32O2P2Se4NH4]: 773.8898.
[1] T.S. Lobana, J.C. Wang, C.W. Liu, Coord. Chem. Rev. 251 (2007) 91.
[2] W. Kuchen, B. Knop, Angew. Chem., Int. Ed. 3 (1964) 507.
[3] W. Kuchen, B. Knop, Angew. Chem., Int. Ed. 4 (1965) 244.
[4] R.P. Davies, M.G. Martinelli, Inorg. Chem. 41 (2002) 348.
[5] R.P. Davies, M.G. Martinelli, A.E.H. Wheatley, A.J.P. White, D.J. Williams, Eur. J.
Inorg. Chem. (2003) 3409.
[6] R.P. Davies, C.V. Francis, A.P.S. Jurd, M.G. Martinelli, A.J.P. White, D.J. Williams,
Inorg. Chem. 43 (2004) 4802.
[7] B.K. Santra, B.J. Liaw, C.M. Hung, C.W. Liu, Inorg. Chem. 42 (2003) 8866.
[8] C.W. Liu, H.C. Chen, J.C. Wang, T.C. Keng, Chem. Commun. (1998) 1831.
[9] C.W. Liu, H.C. Chen, J.C. Wang, T.C. Keng, Chem. Commun. (1999) 995.
[10] C.W. Liu, C.M. Hung, H.C. Chen, J.C. Wang, T.C. Keng, K. Guo, Chem. Commun.
2000 (1897).
3.2.10. O,O0-Dipropyl-Se,Se0-1,4-
[11] C.W. Liu, I.J. Shang, C.M. Hung, J.C. Wang, T.C. Keng, J. Chem. Soc., Dalton Trans.
(2002) 1974.
phenylenebis(methylene)bis(phenylphosphonodiselenoate) (3j)
To dried propanol solution (20 cm3) at room temperature under
nitrogen was added a small piece of sodium (46 mg, 2.0 mmol).
The mixture was stirred for 2 h and became clear colorless solu-
tion. Then, Woollins’ reagent (0.54 g, 1.0 mmol) was added and
the mixture was stirred at room temperature for 2 h. Then 1,3-
dibromopropane (0.264 g, 1.0 mmol) was added and the mixture
was continued stirring for 20 h. After filtered to remove unreacted
solid, the crude product obtained on removal of solvent and puri-
fied by column chromatography, eluted with dichloromethane to
give colorless oil (0.550 g, 73% yield). Selected IR (KBr, cmꢀ1):
1510(w), 1476(m), 1436(m), 1385(m), 1104(m), 979(vs), 833(m),
745(m), 688(m), 551(vs), 498(s). 1H NMR (CD2Cl2, d), 7.95–7.87
(m, 4H, Ar-H), 7.50–7.44 (m, 6H, Ar-H), 7.05 (d, J(H,H) = 7.4 Hz,
4H, Ar-H), 4.19–3.80 (m, 8H, OCH2 + SeCH2), 1.76–1.65 (m, 4H,
CH2), 1.00–0.94 (m, 6H, CH3) ppm. 13C NMR (CD2Cl2, d), 136.9 (d,
J(P,C) = 4.2 Hz), 136.6 (d, J(P,C) = 99.7 Hz), 132.4 (d, J(P,C) = 3.1 Hz),
130.3 (d, J(P,C) = 12.5 Hz), 129.3, 128.6 (d, J(P,C) = 14.5 Hz), 68.3 (d,
J(P,C) = 6.2 Hz, O–C), 35.6 (d, J(P,C) = 4.2 Hz, Se–C), 23.3 (d,
J(P,C) = 9.3 Hz, CH2), 10.3 (CH3) ppm. 31P NMR (CD2Cl2, d), 80.2 (s,
J(P,Seendo) = 446 Hz, J(P,Seexo) = 825 Hz) pm. 77Se NMR (CD2Cl2, d),
412.9 (d, J(P,Seendo) = 444 Hz), ꢀ88.1 (d, J(P,Seexo) = 825 Hz) ppm.
MS (CI+, m/z), 774 [M+NH4]+. Accurate mass measurement (CI+MS):
773.8894 [M+NH4]+, calculate mass for [C26H32O2P2Se4NH4]:
773.8898.
[12] C.W. Liu, C.M. Hung, J.C. Wang, T.C. Keng, J. Chem. Soc., Dalton Trans. (2002)
3482.
[13] C.W. Liu, C.M. Hung, B.K. Santra, J.C. Wang, H.M. Kao, Z. Lin, Inorg. Chem. 42
(2003) 8551.
[14] C.W. Liu, C.M. Hung, B.K. Santra, H.C. Chen, H.H. Hsueh, J.C. Wang, Inorg. Chem.
42 (2003) 3216.
[15] C.W. Liu, C.M. Hung, H.C. Haia, B.J. Liau, L.S. Liou, Y.F. Tsai, J.C. Wang, Chem.
Commun. (2003) 976.
[16] G. Hua, J.D. Woollins, Angew. Chem., Int. Ed. 48 (2009) 1368.
[17] C.J.A. Gomez, R.M. Romano, H. Beckers, H. Willner, V.C.O. Della, Inorg. Chem.
49 (2010) 9972.
[18] G. Hua, A.L. Fuller, Y. Li, A.M.Z. Slawin, J.D. Woollins, New J. Chem. 34 (2010)
1565.
[19] M. Abdo, Y. Zhang, V.L. Schramm, Org. Lett. 12 (2010) 2982.
[20] Y. Huang, G. Jahreis, C. Luecke, D. Wildemann, G. Fischer, J. Am. Chem. Soc. 132
(2010) 7578.
[21] G. Hua, A.L. Fuller, A.M.Z. Slawin, J.D. Woollins, Eur. J. Org. Chem. (2010) 2607.
[22] G. Hua, J.B. Henry, Y. Li, A.R. Mount, A.M.Z. Slawin, J.D. Woollins, Org. Biomol.
Chem. 8 (2010) 1655.
[23] G. Hua, Q. Zhang, Y. Li, A.M.Z. Slawin, J.D. Woollins, Tetrahedron 65 (2009)
6074.
[24] G. Hua, Y. Li, A.L. Fuller, A.M.Z. Slawin, J.D. Woollins, Eur. J. Org. Chem. (2009)
1612.
[25] G. Hua, A.L. Fuller, A.M.Z. Slawin, J.D. Woollins, Polyhedron 30 (2011) 805.
[26] G. Hua, A.L. Fuller, A.M.Z. Slawin, J.D. Woollins, Eur. J. Org. Chem. (2011) 3067.
[27] G. Hua, J.M. Griffin, S.E. Ashbrook, A.M.Z. Slawin, J.D. Woollins, Angew. Chem.,
Int. Ed. 50 (2011) 4123.
[28] G. Hua, D.B. Cordes, Y. Li, A.M.Z. Slawin, J.D. Woollins, Tetrahedron Lett. 52
(2011) 3311.
[29] I.P. Gray, P. Bhattacharyya, A.M.Z. Slawin, J.D. Woollins, Chem. Eur. J. 11 (2005)
6221.
[30] I.P. Gray, A.M.Z. Slawin, J.D. Woollins, Dalton Trans. (2005) 2188.
[31] P. Kilian, P. Bhattacharyya, A.M.Z. Slawin, J.D. Woollins, Eur. J. Inorg. Chem.
(2003) 1461.
Acknowledgement
[32] K. Karaghiosoff, K. Eckstein, Phosphorus, Sulfur Silicon Relat. Elem. 75 (1993)
257.
[33] M.J. Pilkington, A.M.Z. Slawin, D.J. William, D.J. Woollins, Heteroatom. Chem. 1
(1990) 351.
The authors are grateful to the University of St. Andrews for
financial support.