Reactions of naphthyl tellurium trihalides with some dithiocarbamates and xanthates: X-ray structure of t-shaped naphthyl tellurium 1-pyrrolidinecarbodithioate

Article abstract of DOI:10.1080/10426500802202063

The reaction of naphthyl tellurium trihalides, ArTeX3 (X = Br, Cl; Ar = naphthyl) with several salts of dithiocarbamate and xanthate ligands (L) have been investigated by metathesis in tetrahydrofuran. The products (1-3) were characterized by multinuclear NMR spectroscopy and elemental analysis. Crystals of ArTeL (L = 1-pyrrolidine-carbodithioate, 1) were obtained from the reaction of ArTeCl3 and 3 equivalents of NH4[S2CNC4H8]. The structure shows a three-coordinate T-shaped tellurium(II) geometry with one short and one long Te-S bond: the two independent molecules in the unit cell have Te-S distances of 2.444(3) , 2.494(3) and 3.271(5) , 3.042(5) respectively, the latter two distances being intermolecular. The intermolecular interactions and the NMR spectra are discussed, together with a structural comparison of related Te(II) complexes.

Full text of DOI:10.1080/10426500802202063

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Phosphorus, Sulfur, and Silicon
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Reactions of Naphthyl
Tellurium Trihalides with
Some Dithiocarbamates and
Xanthates: X-Ray Structure of
“T-Shaped” Naphthyl Tellurium
1-Pyrrolidinecarbodithioate
Martin D. Rudd a , Angela Defferding a & Kevin K.
Klausmeyer b
a Department of Chemistry , University of
Wisconsin–Fox Valley , Menasha, Wisconsin, USA
b Department of Chemistry and Biochemistry ,
Baylor University , Waco, Texas, USA
Published online: 24 Sep 2008.
To cite this article: Martin D. Rudd , Angela Defferding & Kevin K. Klausmeyer
(2008) Reactions of Naphthyl Tellurium Trihalides with Some Dithiocarbamates
and Xanthates: X-Ray Structure of “T-Shaped” Naphthyl Tellurium 1-
Pyrrolidinecarbodithioate, Phosphorus, Sulfur, and Silicon and the Related Elements,
183:10, 2361-2372, DOI: 10.1080/10426500802202063
To link to this article: http://dx.doi.org/10.1080/10426500802202063
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Phosphorus, Sulfur, and Silicon, 183:2361–2372, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802202063
Reactions of Naphthyl Tellurium Trihalides with Some
Dithiocarbamates and Xanthates: X-Ray Structure
of “T-Shaped” Naphthyl Tellurium
1-Pyrrolidinecarbodithioate
Martin D. Rudd,1 Angela Defferding,1
and Kevin K. Klausmeyer2
1Department of Chemistry, University of Wisconsin–Fox Valley,
Menasha, Wisconsin, USA; 2Department of Chemistry and
Biochemistry, Baylor University, Waco, Texas, USA
The reaction of naphthyl tellurium trihalides, ArTeX3 (X = Br, Cl; Ar = naphthyl)
with several salts of dithiocarbamate and xanthate ligands (L) have been investi-
gated by metathesis in tetrahydrofuran. The products (1–3) were characterized by
multinuclear NMR spectroscopy and elemental analysis. Crystals of ArTeL (L =
1-pyrrolidine-carbodithioate, 1) were obtained from the reaction of ArTeCl3 and 3
equivalents of NH4 [S2 CNC4 H8 ]. The structure shows a three-coordinate T-shaped
tellurium(II) geometry with one “short” and one “long” Te-S bond: the two indepen-
dent molecules in the unit cell have Te-S distances of 2.444(3) Å, 2.494(3) Å and
3.271(5) Å, 3.042(5) Å respectively, the latter two distances being intermolecular.
The intermolecular interactions and the NMR spectra are discussed, together with
a structural comparison of related Te(II) complexes.
Keywords Coordination; dithiocarbamate; tellurium; X-ray structure
INTRODUCTION
As part of our investigation into the coordination chemistry of Te(II)
and Te(IV), we have used a naphthyl group in some of our stud-
ies of new complexes with sulfur and selenium containing ligands.
In a recent article, we described the T-shaped structures of two
thiourea complexes of Te(II), namely [(naphthyl)TeBr(thiourea)] and
Received 18 March 2008; accepted 14 May 2008.
M.D.R. would like to thank the Professional Development Committee at the Univer-
sity of Wisconsin–Fox Valley for generous funding of this undergraduate research and
for travel funds. We would also like to acknowledge Dr. Jerry Lokensgard (Lawrence
University, Appleton) for assistance with the NMR spectra.
Address correspondence to Martin D. Rudd, Department of Chemistry, University of
Wisconsin–Fox Valley, Menasha, WI 54952, USA. E-mail: martin.rudd@uwc.edu
2361

2362
M. D. Rudd et al.
[(naphthyl)TeBr(tetramethylthiourea)],1 and we indicated that there
is a strong trans influence from the aromatic ligand, which leads to
the formation of three-coordinate, rather than four-coordinate struc-
tures. In the literature, there have been some comprehensive reviews
of the structural chemistry of both selenium and tellurium with sulfur
(and selenium) containing ligands: in much of the “organo-coordination”
chemistry of Te(II), the phenyl group or closely related groups have been
employed, presumably because of the availability (or more straightfor-
ward synthesis) of diphenyl ditelluride. In these reviews,2−4 several
complexes of the type [PhTe(L)X] are described, where L = sulfur or se-
lenium monodentate ligand and X = halide with the central tellurium
atoms showing an approximate T-shaped, three-coordinate geometry.
Weak interactions with a fourth “square planar” positioned ligand are
noted in several cases. Interestingly, this structural variation contin-
ues into a range of bidentate ligands, which were first noted by Huse-
bye et al. in their presentation of xanthates and dithiophosphates as
examples.3−7
In continuation of our investigation of the coordination chemisty of
Te(II), with bulky aromatic ligands, we have prepared a series of naph-
thyl tellurium complexes with dithiocarbamate and xanthate ligands.
SCHEME 1 Synthesis of Te(II) complexes.

T-Shaped Tellurium Carbodithioates
2363
RESULTS AND DISCUSSION
Synthesis
The aromatic tellurium trihalides used here reacted cleanly with three
equivalents of dithiocarbamate or xanthate salts in a variety of or-
ganic solvents forming a precipitate of insoluble halides and the cor-
responding naphthyl tellurium dithiocarbamate or xanthate complex
in fair to good yields. The structures of the new complexes are shown
in Scheme 1. A reduction from Te(IV) to Te(II) has taken place in the
course of the reaction, presumably with a concomitant oxidation of two
molecules of the ligand (resulting in a white precipitate, not isolated)
to form S S bonded species. This has been reported previously for two
related tellurium examples.2,4
Molecular Structure
The structure of one of the two independent molecules of 1 is shown
in Figure 1. The crystals are built up from naphthyl tellurium(II)
1-pyrrolidinecarbodithioate molecules connected through weak inter-
. . . .
molecular Te
S bonds forming a three-coordinate T-shaped molecule.
Table I shows a list of selected bond lengths and angles. Firstly, the bond
angle C(6)-Te(1)-S(1) of 85.1(2)◦ is considerably smaller than in related
angular tellurium(II) structures; for instance in the structure of 4-
CH3OC6H4TeSC(S)OCH3 (4-methoxyphenyl tellurium(II) methylxan-
thate) reported by Husebye an angle of 97.24(8)◦ is observed.5
Tellurium Ligand Bonding
Table II compares some of the structural features from related
molecules and the present work. There are notable features that can
TABLE I Selected Bond Lengths (Å) and Angles (◦) for
Compound 1
Te(1)-C(6)
Te(1)-S(1)
Te(2)-C(21)
Te(2)-S(3)
S(1)-C(1)
2.140(9)
2.444(3)
2.139(8)
2.494(3)
1.749(8)
1.700(8)
1.749(8)
1.693(8)
3.042(5)
3.271(5)
C(6)-Te(1)-S(1)
C(21)-Te(2)-S(3)
C(1)-S(1)-Te(1)
C(16)-S(3)-Te(2)
C(1)-N(1)-C(5)
C(1)-N(1)-C(2)
C(5)-N(1)-C(2)
C(16)-N(2)-C(17)
C(16)-N(2)-C(20)
S(2)-C(1)-S(2)
85.1(2)
84.2(2)
100.6(3)
99.4(3)
124.4(7)
123.6(7)
112.0(7)
125.4(7)
122.6(7)
121.3(5)
S(2)-C(1)
S(3)-C(16)
S(4)-C(16)
Te(2)-S(2)
Te(1)-S(3)

2364
M. D. Rudd et al.
FIGURE 1 Molecular structure of one of the independent molecules of 1 in
the crystal. Displacement ellipsoids are shown at the 30% probability level.
be determined from the data and the literature. The two examples in
Table II of coordinated dimethyldithiophosphate ligands to Te(II) both
exhibit a three-coordinate T-shaped type of geometry at the tellurium
atom, that is also seen in 1. In all cases, there is a short (ca. 2.4 Å) Te-S
bond and an additional long (more than 3.0 Å) Te-S interaction with
STeS angles of approximately 170◦. These compounds can be thought
of as 3c-4e models. Examples of methylxanthate ligands coordinated
to Te(II) are also displayed but these show a rather different type of
geometry. In addition to a coordinated sulfur atom with a Te-S distance
of around 2.4 Å, there are two longer interactions to other xanthate
ligands forming a distorted square planar geometry at the tellurium
. . . .
atom—–in the two molecules presented here, the Te
S bonds lay
between ca 3.4–3.7 Å. Furthermore, another two examples from the
literature reveal that Te(II) coordination to a methylthiosulfate ligand
gives a two-coordinate (angular) geometry at tellurium, in which there
is no structural evidence of a third weak interaction with a distant
ligand. Interestingly, the Te S bond distances in these three different

T-Shaped Tellurium Carbodithioates
2365
geometric structures are close to 2.4 Å. In compound 1, the two inde-
pendent molecules exhibit a three-coordinate T-shaped geometry at the
tellurium atom, similar to that described with the dimethyldithiophos-
phate ligands. The Te–S bonds of 2.444(3) and 2.494(3) Å are slightly
longer than many of the examples presented here, but these are well
within the usual range found in the literature; the two longer interac-
tions are at 3.271(5) and 3.042(5) Å, respectively. In the second of these
independent molecules, the sum of the Te-S distances is only 5.536 Å
and thus, considerably shorter than 5.871 Å seen in a related literature
example.5 Figure 2 shows the intramolecular interactions of the pairs
of independent molecules. As can be seen, a single sulfur atom from
a dithiocarbamate ligand forms two links to two adjacent Te atoms
(“short” and “long”). The distance Te(2)· · ·S(2) at 3.042(5) Å (“shorter”)
lies opposite the “longer” Te(2)-S(3) [2.494(3) Å] interaction at a bond
angle of ca. 167◦. Conversely, the distance Te(1)-S(3) measures 3.271(5)
Å (“longer”) and is found ca. 170◦ from the related “shorter” Te(1)-S(1)
distance at 2.444(3) Å. Thus, a twelve-membered linkage of Te, S, and
C atoms is assembled from the independent molecules.
Within the ligand itself, there are the expected differences in C–
S bond lengths that are reflected in the coordination of sulfur;5 in
fact, three different coordination environments are observed for sul-
fur. The sulfur atoms bonded to Te [either S(1) or S(3)] in the “short
bonds” exhibit the greatest elongation of their carbon-sulfur length to
1.749(8) Å (in both cases, and consistent with previous bonding exam-
ples), whereas the sulfur atom [S(2)], that is “more C=S in nature,”
shows a bond length of 1.700(8) Å, well within the ranges typically
seen.2 The “uncoordinated” C=S bonds [C(16)-S(4) 1.693(8) Å] are the
strongest of the three types exhibited in the molecular structure. It
should be noted that one dithiocarbamate ligand has both its sulfur
atoms [S(1) and S(2)] coordinated to two different Te atoms whereas
the other ligand coordinates to two tellurium atoms via a single sul-
fur atom, S(3). The sums of the two Te-S-C-(S)-Te bridges are 8.935
Å [Te(1)-S(1)-C(1)-S(2)-Te(2)] and 9.207 Å [Te(2)-S(3)-C(16)-S(4)-Te(1)],
and this is reflected in the two very dissimilar Te-Te distances in the as-
sembly via the S(1)-S(2) linkage the Te(1)-Te(2) distance is 5.098 Å, but
through the doubly coordinated S(3) atom, the Te(1)-Te(2) distance is
only 4.358 Å. With the current literature in this area, it is not possible to
compare 1 with corresponding three-coordinate T-shaped molecules as
these examples here represent the first T-shaped molecules containing
dithiocarbamate ligands. Table II indicates that with dimethyldithio-
phosphate ligands typically this type of structure is found. Figure 3
shows the basic structural types of divalent Te(II) complexes discussed
in this section.

2366

T-Shaped Tellurium Carbodithioates
2367
FIGURE 2 Packing diagram for 1 showing the T-shaped three-coordinate ge-
ometry of the tellurium atom.
NMR Spectroscopy
1
The H and 13C NMR spectra for the newly synthesized compounds
show the expected signals from both the coordinated sulfur ligands,
and the aromatic naphthyl group coordinated to the tellurium atom.
For instance in 1, the signals of the 1-pyrrolidine-carbodithioate pro-
tons are located at 2.10 and 3.61 ppm as multiplets. The corresponding
NMR signals of the carbon atoms appear at 25 ppm and 52 ppm. The
signal of the dithiocarbamato carbon atom appears well downfield at
ca. 190 ppm, which is typical of coordination in such complexes. The
other compounds display similar characteristics; in compound 2, there
are a large number of aromatic signals from the two phenyl rings of
the dithiocarbamate and the naphthyl group together with a signal at
5.09 ppm resulting from the benzyl methylene hydrogen atoms. In com-
pound 3, the 13C NMR signal of the coordinated xanthate ligand is well
downfield at ca. 210 ppm. For all previously reported two-coordinate

2368

T-Shaped Tellurium Carbodithioates
2369
angular, “T,” and distorted square planar complexes containing this
type of “anionic” ligand no NMR studies were conducted. The chemical
shifts are however in agreement with those reported for similar com-
plexes with neutral thio- or selenoureas coordinated to Te(II).1,6 The
relative simplicity of the spectra and the elemental analyses confirm
the 1:1 ratio of the naphthyl tellurium (ligand) formulation.
EXPERIMENTAL
General
All experiments were performed on a Schlenk line equipped with a
supply of dried argon gas and a vacuum pump. Melting points were
recorded on a Meltemp 4000 and are uncorrected. NMR spectra were
recorded on a Bruker AMX 250 in CDCl3 with TMS as internal stan-
dard unless otherwise indicated. The operating frequency of the in-
strument was 250 MHz for 1H and 62.8 MHz for 13C. All solvents were
of commercial grade and were used as received from Fisher Chem-
ical Co. Naphthyl tellurium trichloride was prepared according to a
literature method;7 naphthyl tellurium tribromide and the dithiocar-
bamate/xanthate salts were purchased from Aldrich Chemical Co. El-
emental analyses were performed by Atlantic Microlab Inc. (Norcross,
GA).
Synthesis of [(C10H7)Te(S 2CNC4H8)] (1)
This product can be prepared from either naphthyl tellurium trichlo-
ride or naphthyl tellurium tribromide. One of the reactions is shown
here as an example. To a solution of naphthyl tellurium trichloride
(0.100 g, 0.27 mmol) in tetrahydrofuran (10 mL) was added a solu-
tion of ammonium 1-pyrrolidinecarbodithioate (0.136 g, 0.83 mmol) in
the same solvent (10 mL). The reaction mixture was vigorously stirred
for 10 min during which time a white precipitate formed in the or-
ange solution. After filtration, the solvent was removed in vacuo, and
the orange-red oil was dissolved in methylene chloride (3 mL). Upon
cooling at −20◦C a crop of red crystals formed together with an insol-
uble white precipitate. Yield: 0.125 g, (71%); m.p.: 105–107◦C. Calcd.
(found) for C31H32Cl2N2S4Te2: C 42.0 (42.0); H 3.64 (3.71); N 3.16 (3.33).
1H NMR: 2.10 [m, 4H, N(CH2)2(CH2)2]; 3.61 [m, 4H, N(CH2)2(CH2)2],
7.29–8.12 [m, 7H, arom-H]; 13C NMR: 25.0 [s, N(CH2)2(CH2)2], 51.2 [s,
N(CH2)2(CH2)2], 119.2, 121.6, 125.1, 126.9, 127.7, 129.3, 132.1, 136.0,
189.7 [s, CS2-pyrrol].

2370
M. D. Rudd et al.
Synthesis of [(C10H7)Te(S 2COC6H13)] (2)
To a solution of naphthyl tellurium trichloride (0.100 g, 0.27 mmol) in
methanol was added a suspension of potassium hexylxanthate (0.147
g, 0.83 mmol) in the same solvent (20 mL). The reaction was warmed
to 50◦C for 1 h and filtered at 30◦C. The solvent was removed in vacuo
and the residue dissolved in methylene chloride (10 mL). Addition of
n-hexane afforded a pale yellow microcrystalline solid. Yield: 0.105 g,
65%; m.p.: 145–147◦C. Calcd. (found) for C17H20OS2Te: C 47.3 (47.2); H
4.66 (4.70). 1H NMR: 0.88 [t, J = 6.0 Hz, 3H, CH3], 1.50 [m, 4H, (CH2)2],
1.88 [m, 4H, (CH2)2], 4.68 [t, J = 6.0 Hz, 2H, O-CH2], 7.31–8.38 (m, 7H,
naphthyl); 13C NMR: 14.1 [s, CH3], 24.5 [s, CH3 − CH2], 25.6 [s, CH2-
CH2], 29.2 [s, CH2 − CH2], 33.0 [s, CH2CH2-O], 74.4 [s, O-CH2], 122.7,
125.5, 126.2, 127.7, 129.0, 130.3, 134.2, 134.7, 210.7 [CS2-O(CH2)5CH3].
Synthesis of [(C10H7)TeS 2CN(CH2C6H5)2] (3)
Naphthyl tellurium tribromide (0.060 g, 0.16 mmol) was dissolved in
methylene chloride (20 mL). To this solution, with vigorous stirring,
was added a solution of sodium dibenzyldithiocarbamate (0.135 g, 0.50
mmol) in methylene chloride (5 mL). The solution immediately became
dark orange and after stirring for 1 h, a fine white precipitate was
filtered out. The solution was concentrated to ca. 2 mL and layered with
n-hexane. After 2 days, a microcrystalline yellow solid was collected
by filtration. Yield: 0.099 g, 61%; m.p.: 188–192◦C. Calcd. (found) for
C25H21NS2Te: C 57.0 (57.1); H 4.01 (4.09); N 2.66 (2.73). 1H NMR: 5.09
[s, 4H, CH2-Ph], 7.20–8.36 [m, 17H, Ph and naphthyl]; 13C NMR: 55.1
[s, CH2-Ph], 122.6, 124.6, 126.6, 127.2, 127.7, 127.9, 128.5, 129.7, 130.3,
134.1, 139.8, 195.7 [s, CS2].
X-Ray Structure Determination
Crystal data and structure refinement parameters are shown in
Table III. During recrystallization, compound 1 picked up a molecule of
methylene chloride solvent (reflected in elemental analysis). Crystal-
lographic data for 1 was collected on a crystal with dimensions 0.185
× 0.105 × 0.105 mm. Data were collected at 110 K on a Bruker X8
Apex diffractometer using MoKα radiation (λ = 0.71073 Å). The struc-
ture was solved by Direct Methods after absorption correction of the
data using SADABS.8 All of the data were processed using the Bruker
AXS SHELXTL software, version 6.10.9 Unless otherwise noted, all

T-Shaped Tellurium Carbodithioates
2371
TABLE III Crystal Structure and Data
Refinement Parameters for Compound 1
Empirical formula
C31H32Cl2N2S4Te2
Formula weight
886.93
Crystal system / space group
Triclinic/P-1
a/Å
b/Å
11.595(8)
11.974(8)
c/Å
α/◦
β/◦
γ/◦
13.888(10)
77.809(14)
65.851(18)
72.678(16)
V/Å3
1671(2)
2
1.763
Z
Dcalc (g/cm3)
µ(mm−1
)
2.181
Crystal size (mm)
Color/shape
0.185 × 0.105 × 0.105
Red/block
Temp (K)
110(2)
Theta range for collection
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness of fit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
2.29 to 26.88
23387
6834
6834/0/370
1.011
R1 = 0.0652 wR2 = 0.1519
R1 = 0.1054 wR2 = 0.1733
1.845/−2.356 e/A3
Largest difference peak/hole
non-hydrogen atoms were refined anisotropically and hydrogen atoms
were placed in calculated positions.
SUPPLEMENTARY MATERIAL
Crystallographic data for the structural analysis of compound 1 has
been deposited at the Cambridge Crystallographic Data Center (CCDC
number 620510). Copies of the information may be obtained free of
charge from The Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (Fax: + 44-1223-336033; email: deposit@ccdc.cam.ac.uk or
www.ccdc.cam.ac.uk).
REFERENCES
[1] M. D. Rudd, D. Pahl, C. Hofkens, and R. Feazell, Phosphorus, Sulfur, and Silicon,
181, 2023 (2006).

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M. D. Rudd et al.
[2] S. Husebye, In Proceedings of the 4th International Conference on the Organic Chem-
istry of Selenium and Tellurium, F. J. Berry and W. R. McWhinnie, Eds. (The Uni-
versity of Aston, Birmingham, 1983), p. 298.
[3] S. Husebye, K. Martmann-Moe, and Ø. Mikalsen, Acta Chem. Scand., 43, 754, (1989).
[4] J. Novosad, S. V. Lindeman, J. Marek, J. D. Woollins, and S. Husebye, Heteroatom
Chem., 9, 615 (1998).
[5] L. Pauling, The Nature of the Chemical Bond (Cornell University Press, New York,
1960), 3rd ed., p. 224.
[6] G. K. O’Quinn, M. D. Rudd, and J. Kautz, Phosphorus, Sulfur, and Silicon, 177, 853
(2002).
[7] G. T. Morgan and R. E. Kellett, J. Chem. Soc., 1080 (1926).
[8] G. M. Sheldrick, University of Go¨ttingen, Go¨ttingen, Germany, 1997.
[9] G. M. Sheldrick, 6.10 ed.; (Bruker AXS, Inc., Madison, WI, 2000).