Synthesis and characterization of novel organic heteroatom compounds from reaction of Woollins' reagent with various organic substrates

Article abstract of DOI:10.1080/10426507.2015.1072184

A series of new selenium-containing heteroatom compounds were synthesized in good yields by the reaction of Woollins reagent with various organic substrates such as cyclohexylamine, N-benzoylbenzamide, benzoic anhydride, 4-fluoro-N-(2-oxo-2-phenylethyl)benzamide, N-benzoylbenzamide, benzoic anhydride, 3-(bromomethyl)benzonitrile, 1,2-diphenylethane-1,2-diol, and sodium alcoholate. Three representative X-ray structures are described.

Full text of DOI:10.1080/10426507.2015.1072184

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Synthesis and Characterization of Novel Organic
Heteroatom Compounds from Reaction of
Woollins' Reagent with Various Organic Substrates
Guoxiong Hua, Junyi Du, David B. Cordes, Kasun S. A. Arachchige, Alexandra
M. Z. Slawin & J. Derek Woollins
To cite this article: Guoxiong Hua, Junyi Du, David B. Cordes, Kasun S. A. Arachchige,
Alexandra M. Z. Slawin & J. Derek Woollins (2015): Synthesis and Characterization of
Novel Organic Heteroatom Compounds from Reaction of Woollins' Reagent with Various
Organic Substrates, Phosphorus, Sulfur, and Silicon and the Related Elements, DOI:
10.1080/10426507.2015.1072184
To link to this article: http://dx.doi.org/10.1080/10426507.2015.1072184
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Synthesis and Characterization of Novel Organic Heteroatom Compounds
from Reaction of Woollins’ Reagent with Various Organic Substrates
Guoxiong Hua, Junyi Du, David B. Cordes, Kasun S. A. Arachchige, Alexandra M. Z. Slawin
and J. Derek Woollins*
EaStCHEM School of Chemistry, University of St Andrews, Fife, KY16 9ST, UK
*Corresponding author. Tel.: (+44)-1334-463384; email: jdw3@st-and.ac.uk
Abstract
A series of new selenium-containing heteroatom compounds were synthesized in good yields by
the reactions of Woollins’ reagent with various organic substrates such as cyclohexylamine, N-
benzoylbenzamide, benzoic anhydride, 4-fluoro-N-(2-oxo-2-phenylethyl)benzamide, N-
benzoylbenzamide, benzoic anhydride, 3-(bromomethyl)benzonitrile, 1,2-diphenylethane-1,2-
diol and sodium alcoholate. Three representative X-ray structures are described.
CN
O
O
O
O
Se
Se
O
Se
CN
O
Se
Se
Se
Ph
Ph
Se
Ph
Ph
Se
O
Se
Se
P
P
P
Ph
O
O
Woollins' Reagent
Ph
O
P
Se
P
NH
Te
Te
Ph
O
Ph
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Key words
Woollins’ reagent / Benzamides / Diselenoperoxyanhydrides / Heteroatom compounds / Single
crystal structures
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INTRODUCTION
Following the discovery of seleno-enzymes, selenium-containing compounds have been studied
extensively because of their interesting reactivity profile and potential applications in many areas
such as organic synthesis,1 biochemistry,2 xerography,3 the synthesis of conducting materials,4
semiconductors,5 ligand synthesis6 and cancer therapy.7 A wide range of selenation reagents can
introduce selenium into organic substrates by both nucleophilic and electrophilic pathways, and
the resulting selenium-containing products can be further converted into useful targets that may
or may not retain the selenium atom.8 2,4-Bis(phenyl)-1,3-diselenadiphosphethane-2,4-diselenide
[{PhP(Se)(µ-Se)}2] (Woollins’ reagent, WR, a selenium counterpart of Lawesson’s reagent) has
proved in recent years to be an efficient selenation reagent in organic synthetic chemistry due to
its ready preparation and ease of handling.9-21 Herein, we report the synthesis of a series of novel
selenium-containing heteroatom compounds from the reaction of Woollins’ reagent with various
organic substrates such as alkylamine, benzamides, benzoic anhydride, benzonitrile, 1,2-diol,
sodium alkyl-alcoholate and three representative single crystal X-ray structures.
RESULTS AND DISCUSSION
Treatment of Woollins’ reagent with an equi-molar amount of N-benzoylbenzamide (1)22 in
refluxing toluene solution led to the formation of benzoic diselenoperoxyanhydride (2) in 53%
isolated yield. Alternatively, applying Woollins’ reagent with an equivalent of benzoic anhydride
under identical conditions gave the same product (2) in 72% isolated yield (Scheme 1). This
efficient method is very simple and easy to control, and avoids using harsh selenation reagents
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such as LiAlHSeH for the synthesis of various diacyl selenides, diacyl diselenides and
selenocarboxylates.23
Similarly, furan-2-carboxylic diselenoperoxyanhydride (4) could be prepared by the reaction
of Woollins’ reagent with an equi-molar amount of N-(furan-2-carbonyl)furan-2-carboxamide
(3)24 under identical conditions in 61% isolated yield (Scheme 2). We confirmed the nature of 4
by a single crystal X-ray structure obtaining similar results to those reported elsewhere.25
An attempt to synthesize selenoamide (5) by treating 3-(bromomethyl)benzonitrile with
Woollins’
reagent/H2O
in
refluxing
toluene
failed,
instead,
3,3'-
(diselanediylbis(methylene))dibenzonitrile (6) was unexpectedly isolated in excellent yield (93%)
as shown in Scheme 3. The result is in contrast with the previous report that the nitrile reacted
with Woollins’ reagent/H2O leading to the formation of 3-(bromomethyl)benzoselenoamide
(5).26 Surprisingly, 3,3'-(diselanediylbis(methylene))dibenzonitrile (6) formed with the CN
group being intact. The mechanism for this reaction is not clear so far and further investigation is
underway. The IR spectrum of 6 shows a strong band at 2225 cm-1 resulting from the v(C-N) and
is characteristic of the C≡N group. The 77Se NMR spectrum of 6 displays a singlet signal at
419.0 ppm, comparable to the related diselenides.27 A single crystal structure confirmed the
formation of the compound 6 (Figure 1).28
Breaking the four-membered ring in Woollins’ reagent with two molar equivalents of sodium
methanolate generated the sodium O-methyl phenylphosphonodiselenoate 7;29 the latter was
further stirred with an equivalent of trichloro(p-tolyl)-λ4-tellane in dry THF for 24 h at room
temperature delivering bis(p-tolyltellanyl)selane (8) in 47% isolated yield as depicted in Scheme
4. Compound 8 was spectrally characterized by multi-nuclear NMR and IR spectroscopy and
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accurate mass measurement. Two stereoisomers were observed from multinuclear NMR spectra
which show very close chemical shifts in both the 77Se NMR spectrum (δSe 265.4 and 265.5 ppm)
and the 125Te NMR spectrum (δTe 423.5 and 423.8 ppm). According to the literature, compound
8 is new though similar compounds can be obtained by reaction of diaryl ditelluride with SeO2
in pyridine.30 However, we have found no published X-ray crystal structure data for this kind of
compound, therefore, we report the new single crystal structure here (Figure 2).28 The single
crystal structure adopts a symmetric framework. The Te-Se single bond length [2.5216(16) Å] is
significantly longer than the Se-Se single bond distance [2.3088(9) Å] in the structure of 6,
reflecting the big difference of the formation of the single bond between a selenium atom and a
tellurium atom.
Stirring a mixture of diphenylethane-1,2-diol with an equimolar amount of Woollins’ reagent
in refluxing toluene for 3 h afforded two five-membered heterocycles 9 and 10 in 14% and 31%
yields, respectively, after work up in air (Scheme 5). We presume that Woollins’ reagent in
toluene solution at elevated temperature is in equilibrium with a diselenaphosphorane PhP(Se)2
(I), which is believed to be a true reactive species (Scheme 6).31 We suggest that the initial step
involves the reaction of intermediate I with diphenylethane-1,2-diol to give a five-membered
ring 9 via an intramolecular cyclization by eliminating a molecule of H2Se; then, compound 9
could be readily oxidized by air to give another five-membered ring 10 (Scheme 6).
Monophosphorus 9 and 10 are soluble in organic solvents and air-stable. The 31P NMR spectra
of 9 and 10 show sharp singlets at 107.9 and 34.9 ppm, however, one pair of satellites for the
exocyclic selenium atom [(1J(P,Seexo): 925 Hz] was only found in 9, thus indicating the presence
77
of the double P=Se bond in this structure. The Se NMR spectrum of 9 contains one doublet
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signal (δSe = -186.0 ppm) with a matching coupling constant further confirming the presence of
the only P=Se double bond. The single crystal X-ray structure has been reported elsewhere32 and
confirmed the formation of compound 10.
Reaction of Woollins’ reagent with two molar equivalents of cyclohexylamine at room
temperature for 1 h gave the ammonium phenylphosphonamidodiselenoates 11 in almost
quantitative yield;22 the latter was further treated with one molar equivalent of
chlorodiphenylphosphane but did not result in the expected compound 12, instead N-cyclohexyl-
P,P-diphenylphosphinoselenoic amide (13) formed in 72% isolated yield as displayed in Scheme
31
7. The P NMR spectrum has a sharp singlet at 54.4 ppm, which is accompanied by one set of
satellite for the exocyclic selenium atom [(1J(P,Seexo): 751 Hz], indicating the presence of double
77
P=Se bond. The Se NMR spectrum reveals a set of signals at δSe = -252.7 Hz with matching
coupling constant further confirming the presence of only the P=Se double bond. Single crystal
structure analysis further confirmed the formation of the compound 13 (Figure 3).28 The single
crystal structure of 13 adopts a distorted tetrahedral conformation. The dihedral angles between
the mean plane of cyclohexyl ring and two phenyl rings are 86.3 and 36.0°. The P(1)-Se(1)
distance [2.139(3) Å] is marginally longer than the normal P=Se double bond length [ca. 2.08
Å]33 and the P–N single bond length [1.672(7) Å] is significantly shorter, compared to the other
typical P–N single bond system [ca. 1.80 Å],34 suggesting some delocalization.
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
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1
13
up procedures were performed in air. H (400.1 MHz), C (100.6 MHz), 31P-{1H} (162.0 MHz)
º
and 77Se-{1H} (51.5 MHz referenced to external Me2Se) NMR spectra were recorded at 25 C
(unless stated otherwise). IR spectra were recorded as KBr pellets in the range of 4000-250 cm-1
on a Perkin-Elmer 2000 FTIR/Raman spectrometer. Mass spectrometry was performed by the
EPSRC National Mass Spectrometry Service Centre, Swansea. X-ray crystal structures were
determined for compounds 6, 8 and 13 at -148(1) °C on a Rigaku ACTOR-SM, Saturn 724 CCD
area detector [the St Andrews Automated Robotic Diffractometer (STANDARD)]27a with
SHINE optic using Mo Ka radiation (λ = 0.71073 Å). The data were corrected for Lorentz,
polarisation and absorption. The data was collected and processed using CrystalClear (Rigaku).35
The structures were solved by direct methods36 and expanded using Fourier techniques.37
Hydrogen atoms were refined using the riding model. All calculations were performed using the
CrystalStructure38 and SHELXL 97.39 These data can be obtained free of charge via
www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge Crystallographic Data centre,
12 Union Road, Cambridge CB2 1EZ, UK; fax (+44) 1223-336-033; e-mail:
deposit@ccdc.cam.ac.uk. CCDC 1054712-1054714. The Supplemental Materials contains
sample 1H and 13C spectra for compounds 2, 6, 8, 9, 10 and 13 (Figures S 1 – S 12)
Benzoic diselenoperoxyanhydride (2). Method 1
A suspension of N-benzoylbenzamide (0.225 g, 1.0 mmol) and Woollins’ reagent (0.54 g, 1.0
mmol) in toluene (15 mL) was refluxed for 15 h. Upon cooling to room temperature and
removing toluene the residue was dissolved in dichloromethane and purified by silica gel
(dichloromethane as eluent) to afford the titled compound 2 as yellow solid (0.194 g, 53%).
Method 2: A red suspension of benzoic anhydride (0.226 g, 1.0 mmol) and Woollins’ reagent
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(0.54 g, 1.0 mmol) in dry toluene (20 mL) was refluxed for 15 h. Upon cooling to room
temperature and removing toluene in vacuum, the residue was purified by silica gel column
(dichloromethane as eluent) to give the titled compound 2 as yellow solid (0.266 g, 72%). M.p.
130-132 ˚C. Selected IR (KBr, cm-1): 1738(m), 1685(s), 1444(m), 1196(s), 1173(m), 866(s),
1
769(m), 686(m), 664(s). H NMR (CD2Cl2, δ), 8.00 (d, J(H,H) = 7.6 Hz, 4H, Ar-H), 7.65 (t,
J(H,H) = 7.6 Hz, 2H, Ar-H), 7.53 (t, J(H,H) = 7.6 Hz, 4H, Ar-H) ppm. 13C NMR (CD2Cl2, δ),
77
187.2, 136.8, 134.5, 129.1, 128.1 ppm. Se NMR (CD2Cl2, δ), 614.1 ppm. MS (CI+, m/z), 371
[M+H]+. Anal. Calcd. for C14H10O2Se2 (368.15): C, 45.7; H, 2.7. Found: C, 46.0; H, 2.8.
Furan-2-carboxylic diselenoperoxyanhydride (4)
A red suspension of N-(furan-2-carbonyl)furan-2-carboxamide (0.205 g, 1.0 mmol) and
Woollins’ reagent (0.54 g, 1.0 mmol) in dry toluene (20 mL) was refluxed for 10 h. Upon
cooling to room temperature and removing toluene in vacuum the residue was purified by silica
gel column (1 : 1 hexane / dichloromethane as eluent) to give the titled compound 4 as a pale
yellow solid (0.213 g, 61%). M.p. 156-157 °C. Selected IR (KBr, cm-1): 1740(m), 1683(s),
1
1195(s), 1178(m), 867(s), 770(m), 690(m), 665(s). H NMR (CDCl3, δ), 7.78 (d, J(H,H) = 3.6
Hz, 2H, Furan-H), 7.51 (d, J(H,H) = 3.7 Hz, 2H, Furan-H), 6.65 (dd, J(H,H) = 3.7 Hz, J(H,H) =
3.6 Hz, 2H, Furan-H) ppm. 13C NMR (CDCl3, δ), 155.5, 149.9, 146.1, 124.7, 113.3 ppm. 77Se
NMR (CD2Cl2, δ), 624.5 ppm. Mass spectrum [CI+, m/z]: 351 [M+H]+. Accurate mass
measurement [CI+, m/z]: 350.8667 [M+H]+, calculated mass for C10H7O4Se2H: 350.8673.
3,3'-(Diselanediylbis(methylene))dibenzonitrile (6).
A red suspension of 2-(bromomethyl)benzonitrile (0.195 g, 1.0 mmol) and Woollins’ reagent
(0.54 g, 1.0 mmol) in dry toluene (20 mL) was refluxed for 6 h. Upon cooling to below 100 °C
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water (1.0 mL) was added, the mixture then was allowed to refluxing for another 2 h. After
cooling to room temperature and removing toluene in vacuum the residue was purified by silica
gel column (dichloromethane as eluent) to give the tiled compound 6 as orange solid (0.35 g,
93%). The crystals for X-ray determination were obtained from the diffusion of the
dichloromethane solution of the compound into hexane. M.p. 176-178 °C. Selected IR (KBr, cm-
1): 2225(s), 1579(m), 1478(s), 1415(m), 1292(m), 1177(s), 1087(m), 896(s), 829(m), 801(vs),
688(vs), 532(s), 437(s). 1H NMR (CD2Cl2, δ), 7.82-7.43 (m, 8H, Ar-H)), 3.82 (s, 4H, CH2) ppm.
13C NMR (CD2Cl2, δ), 140.8, 133.3, 132.3, 130.8, 129.4, 118.5, 112.6, 31.1 ppm. 77Se NMR
(CD2Cl2, δ), 419.4 ppm. Mass spectrum [CI+, m/z]: 393 [M+H]+. Accurate mass measurement
[CI+, m/z]: 392.9404 [M+H]+, calculated mass for C16H12N2Se2H: 392.9408.
Synthesis of bis(p-tolyltellanyl)selane (8)
Small pieces of sodium (0.046 g, 2.0 mmol) were stirred in dry methanol (40 mL) at room
temperature until fully dissolved. To this mixture Woollins’ reagent (0.54 g, 1.0 mmol) was
added and continued stirring for 3 h. The resulting green solution was filtered through a small
Celite pad from the reaction mixture. The filtrate was concentrated under vacuum to ca. 5 mL
and hexane (10 mL) was added to precipitate the salt as a white solid. Then, the above salt in
THF (30 mL) was added dropwise to a solution of trichloro(p-tolyl)-λ4-tellane (0.312 g, 1.0
mmol) in THF (20 mL) at room temperature. The mixture was stirred at room temperature for
another 24 h. After removing solvent in vacuum the residue was purified by silica gel column
(dichloromethane as eluent) to give the titled compound 8 as red paste (0.120 g, 47%). Two
diastereomers were found in multi-NMR spectra. Selected IR (KBr, cm-1): 1479(m), 1439(m),
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1
1207(m), 1183(m), 1135(m), 1046(s), 984(s), 796(s), 751(s), 696(s), 560(m), 524(s), 477(m). H
NMR (CD2Cl2, δ), 7.79-7.60 (m, 4Hx2, Ar-H), 7.09-6.99 (m, 4Hx2, Ar-H), 2.37 (s, 3H, CH3),
13
2.30 (s, 3H, CH3) ppm. C NMR (CD2Cl2, δ), 138.3, 138.0, 132.4, 131.4, 131.3, 130.2, 128.6,
128.4, 21.0, 20.9 ppm. 77Se NMR (CD2Cl2, δ), 265.5 and 263.0 ppm. 125Te NMR (CD2Cl2, δ),
423.7 and 423.6 ppm. Mass spectrum [CI+, m/z]: 521 [M+H]+. Accurate mass measurement [CI+,
m/z]: 520.8442 [M+H]+, calculated mass for C14H14SeTe2H: 520.8445.
Reaction of Woollins’ Reagent with diphenylethane-1,2-diol
A mixture of diphenylethane-1,2-diol (0.214 g, 1.0 mmol) and Woollins’ reagent (0.54 g, 1.0
mmol) in dry toluene (20 mL) was stirred at room temperature for 3 h. Then the mixture was
heated to 60 ˚C and kept stirring for 2 h. The red suspension disappeared and a greyish green
solution formed. Upon cooling to room temperature and removing the solvent in vacuum the
residue was purified by silica gel column (dichloromethane as eluent) to give the compounds 9
and 10.
2,4,5-Triphenyl-1,3,2-dioxaphospholane 2-selenide (9)
Pale green solid (0.055 g, 14%). M.p. 186-188 °C. Selected IR (KBr, cm-1): 1587(w), 1496(m),
1
1436(m), 1454(m), 1112(m), 980(s), 856(m), 716(s), 692(s), 637(s), 575(m, P=Se). H NMR
(CD2Cl2, δ), 8.10-7.95 (m, 2H, Ar-H), 7.70-7.59 (m, 2H, Ar-H), 7.73-7.15 (m, 11H, Ar-H), 5.89
(dd, J(P,H) = 13.6 Hz, J(H,H) = 2.3 Hz, 2H, CH) ppm. 13C NMR (CD2Cl2, δ), 134.4 (d, J(P,C) =
5.0 Hz), 133.3 (d, J(P,C) = 3.3 Hz), 131.9 (d, J(P,C) = 10.4 Hz), 130.5 (d, J(P,C) = 8.9 Hz),
128.9 (d, J(P,C) = 15.5 Hz), 128.4, 128.0, 126.9, 83.9 ppm. 31P NMR (CD2Cl2, δ), 107.9 (s,
J(P,Se) = 925 Hz) ppm. 77Se NMR (CD2Cl2, δ), -186.0 (d, J(P,Se) = 925 Hz) ppm. Mass
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spectrum [CI+, m/z]: 401 [M+H]+. Accurate mass measurement [CI+, m/z]: 401.0203 [M+H]+,
calculated mass for C20H17O2PSeH: 401.0210.
2,4,5-Triphenyl-1,3,2-dioxaphospholane 2-oxide (10)
Pale white solid (0.105 g, 31%). M.p. 206-207 °C. Selected IR (KBr, cm-1): 1439(m), 1269(m),
1
1133(m), 992(s), 870(m), 840(m), 716(s), 693(s), 510(m). H NMR (CD2Cl2, δ), 8.06-7.94 (m,
2H, Ar-H), 7.71-7.55 (m, 2H, Ar-H), 7.23-7.05 (m, 11H, Ar-H), 6.74 (dd, J(P,H) = 9.2 Hz, J(P,H)
13
= 1.4 Hz, 2H, CH) ppm. C NMR (CD2Cl2, δ), 134.4, 131.9, 130.9, 130.6, 129.1, 128.4, 121.1
31
(d, J(P,C) = 2.4 Hz), 110.5 (d, J(P,C) = 8.3 Hz), 84.0 ppm. P NMR (CD2Cl2, δ), 39.4 ppm.
Mass spectrum [CI+, m/z]: 377 [M+H]+. Accurate mass measurement [CI+, m/z]: 377.0989
[M+H]+, calculated mass for C20H17O3PH: 377.0992.
N-Cyclohexyl-P,P-diphenylphosphinoselenoic amide (13)
A red mixture of cyclohexylamine (0.396 g, 4.0 mmol) and Woollins’ reagent (0.54 g, 1.0 mmol)
in tetrahydrofuran (60 mL) was stirred at room temperature for 1 h. The red suspension became
pale yellow suspension. Then diphenylchlorophosphine (0.600 g, 2. 0 mmol) was added and the
mixture was continued stirring at room temperature overnight. Upon filtering to remove
insoluble solid and drying in vacuum the reside was purified by silica gel column (1 : 1 hexane /
dichloromethane as eluent) to give the titled compound 13 as a greenish yellow paste (0.260 g,
72%). Selected IR (KBr, cm-1): 1477(m), 1434(s), 1306(m), 1180(m), 1097(s), 879(s), 744(s),
689(vs), 540(s), 516(s), 489(s). 1H NMR (CDCl3, δ), 8.02-7.93 (m, 4H, Ar-H), 7.44-7.40 (m, 6H,
Ar-H), 2.30-2.15 (m, 1H, cyclohexyl-H), 1.98 (dd, J(H,H) = 8.0 Hz, 1H, NH), 1.61-1.05 (m, 10H,
cyclohexyl-H) ppm. 13C NMR (CDCl3, δ), 134.7 (d, J(P,C) = 92.4 Hz), 132.4 (d, J(P,C) = 3.1
Hz), 131.8 (d, J(P,C) = 11.4 Hz), 128.4 (d, J(P,C) = 12.5 Hz), 52.1, 35.9, 29.1, 25.5, 25.2 ppm.
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77
31P NMR (CDCl3, δ), 54.4 (s, J(P,Se) = 751 Hz) ppm. Se NMR (CD2Cl2, δ), -252.7 (d, J(P,Se)
= 751 Hz). Mass spectrum [CI+, m/z]: 364 [M+H]+. Accurate mass measurement (CI+): 364.0731,
calculate mass for C18H23NPSe2 [M+H]+: 364.0733.
ACKNOWLEDGEMENTS
We are grateful to the University of St Andrews for financial support and the EPSRC National
Mass Spectrometry Service Centre (Swansea) for mass spectral measurements.
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3311-3314.
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21. Kaschel, J.; Schmidt, C. D.; Mumby, M.; Kratzert, D.; Stalke, D.; Werz, D. B. Chem.
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28. Single crystal structure of 6: yellow prism crystal 0.120 x 0.120 x 0.030 mm, C16H12N2Se2,
M = 390.20, monoclinic, space group P21/n, a = 8.723(3), b = 8.258(2), c = 20.888(7) Å, α =
90°, β = 99.221(10)o, γ = 90o, V = 1485.2(8) Å3, Z = 4, ρcalcd = 1.745 gcm-3, μ = 49.701 cm-1,
9275 reflections collected, 2689 unique [R(int) = 0.0314], R1 = 0.0344, wR2 = 0.0769. CCDC
1054712.
Single crystal structure of 8: red needle crystal 0.100 x 0.020 x 0.010 mm, C14H14SeTe2, M
= 516.42, orthorhombic, space group Pbcn, a = 32.991(14), b = 7. 223(3), c = 6.083(3) Å, α =
90°, β = 90o, γ = 90o, V = 1449.6(11) Å3, Z = 4, ρcalcd = 2.366 gcm-3, μ = 65.132 cm-1, 6774
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reflections collected, 1306 unique [R(int) = 0.0978], R1 = 0.0584, wR2 = 0.1507. CCDC
1054713.
Single crystal structure of 17: colorless chunk crystal 0.210 x 0.110 x 0.070 mm,
C18H21NPSe, M = 361.30, monoclinic, space group C2/c, a = 17.178(8), b = 10.958(5), c =
18.744(11) Å, α = 90°, β = 98.37(3)o, γ = 90°, V = 3491(3) Å3, Z = 8, ρcalcd = 1.375 gcm-3, μ
= 22.371 cm-1, 14083 reflections collected, 3049 unique [R(int) = 0.1317], R1 = 0.0747, wR2 =
0.2569. CCDC 1054714.
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University of Nijmegen, The Netherlands, 1999.
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38. CrystalStructure 3.8.1, Crystal Structure Analysis Package, Rigaku and Rigaku/MSC (2000–
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Figure 1 Single crystal structure of compound 6. Selected bond lengths (Å) and angles (˚) (esds
in parentheses): Se(1)-Se(2) 2.3088(9), C(1)-Se(1) 1.977(3), C(9)-Se(2) 1.992(3); C(1)-Se(1)-
Se(2) 100.97(11), Se(1)-C(1)-C(2) 112.8(2), C(9)-Se(2)-Se(1) 101.95(11), Se(2)-C(9)-C(10)
112.6(2).
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Figure 2 Single crystal structure of compound 8. Selected bond lengths (Å) and angles (˚) (esds
in parentheses): Se(1)-Te(1) 2.5216(16), Te(1)-C(1) 2.130(10); Te(1)-Se(1)-Te(1A) 107.02(9),
C(1)-Te(1)-Se(1) 96.0(3).
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Figure 3 Single crystal structure of compound 13. Selected bond lengths (Å) and angles (˚) (esds
in parentheses): Se(1)-P(1) 2.139(3), P(1)-N(1) 1.672(7), P(1)-C(1) 1.839(9), P(1)-C(7) 1.819(9);
Se(1)-P(1)-N(1) 119.6(3), Se(1)-P(1)-C(1) 1115(3), Se(1)-P(1)-C(7) 112.4(3), N(1)-P(1)-C(1)
104.6(4), N(1)-P(1)-C(7) 102.3(4), C(1)-P(1)-C(7) 105.0(4).
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Scheme 1 Reaction of Woollins’ reagent and N-benzoylbenzamide or benzoic anhydride
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Scheme 2 Reaction of Woollins’ reagent and N-(furan-2-carbonyl)furan-2-carboxamide
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Scheme 3 Reaction of Woollins’ reagent and 3-(bromomethyl)benzonitrile
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Scheme 4. Reaction of Woollins’ reagent and sodium methanolate/ trichloro(p-tolyl)-λ4-tellane
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Scheme 5 Reaction of Woollins’ reagent and 1,2-diphenylethane-1,2-diol
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Scheme 6 Possible mechanism for the formation of compounds 9 and 10
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Scheme 7 Reaction of Woollins’ reagent and cyclohexylamine/chlorodiphenylphosphane
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