Synthesis and structure of group 14 element derivatives of carbotelluroates

Article abstract of DOI:10.1021/om010934b

Group 14 element derivatives of carbotelluroates, RCOTeMPh₃ (M = Ge, Sn, Pb), were synthesized as stable compounds by reacting sodium carbotelluroates with Ph₃MCL and were characterized by IR and ¹³C and ¹²⁵Te NMR spectra. Their molecular structures were revealed by X-ray molecular analysis. The C=O?Sn distance in RCOTeSnPh₃ was found to be shorter than the C=O?Ge distance in RCOTeGePh₃, despite the fact that the atomic radius of Sn is larger than that of Ge. A similar shortening of the nonbonding distance was observed for the corresponding selenium derivatives. Molecular orbital calculations of model compounds, i.e., CH₃COEM(CH₃)₃ (E = Se, Te; M = Ge, Sn, Pb), at the B3LYP/LANL2DZ+p level also supported this shortening of the C=O?Sn distance. NBO (natural bond orbital) analyses of the model compounds showed that two types of orbital interactions, n_o →σ *_ME and n_o→σ *_MC (E = S, Se, Te; M = Ge, Sn, Pb), are important in these carbochalcogenoates. Furthermore, the former interaction has a greater role in the case of carbothioates, whereas the latter is dominant in carbotelluroates.

Full text of DOI:10.1021/om010934b

Organometallics 2002, 21, 1487-1492
1487
Syn th esis a n d Str u ctu r e of Gr ou p 14 Elem en t
Der iva tives of Ca r botellu r oa tes
Kazuyasu Tani, Ryo Yamada, Takahiro Kanda, Masahiro Suzuki,
Shinzi Kato,* and Toshiaki Murai*
Department of Chemistry, Faculty of Engineering, Gifu University,
1-1 Yanagido, Gifu 501-1193, J apan
Received October 29, 2001
Group 14 element derivatives of carbotelluroates, RCOTeMPh3 (M ) Ge, Sn, Pb), were
synthesized as stable compounds by reacting sodium carbotelluroates with Ph3MCl and were
characterized by IR and 13C and 125Te NMR spectra. Their molecular structures were revealed
by X-ray molecular analysis. The CdO‚‚‚Sn distance in RCOTeSnPh3 was found to be shorter
than the CdO‚‚‚Ge distance in RCOTeGePh3, despite the fact that the atomic radius of Sn
is larger than that of Ge. A similar shortening of the nonbonding distance was observed for
the corresponding selenium derivatives. Molecular orbital calculations of model compounds,
i.e., CH3COEM(CH3)3 (E ) Se, Te; M ) Ge, Sn, Pb), at the B3LYP/LANL2DZ+p level also
supported this shortening of the CdO‚‚‚Sn distance. NBO (natural bond orbital) analyses
of the model compounds showed that two types of orbital interactions, nOfσ*ME and nOfσ*MC
(E ) S, Se, Te; M ) Ge, Sn, Pb), are important in these carbochalcogenoates. Furthermore,
the former interaction has a greater role in the case of carbothioates, whereas the latter is
dominant in carbotelluroates.
In tr od u ction
bond(s)4,7-9 have been reported, and in all cases alkyl
and aryl groups are attached to the tellurium atom. In
contrast, no derivatives bearing acyl groups have been
synthesized. This is in part because of the lower stability
of organotellurium compounds. For example, black
tellurium readily deposits from Te-alkyl and Te-aryl
carbotelluroates RCOTeR′ unless they are handled
under an atmosphere of inert gas. Moreover, the ap-
propriate starting materials that lead to group 14
element derivatives of carbotelluroates have not been
developed.10 Recently, we successfully synthesized and
characterized solvent and metal halide free sodium
carbotelluroates.11 We also obtained group 14 element
derivatives of carboselenoate as stable compounds.12 We
report here the first synthesis and the molecular and
electronic structures of group 14 element derivatives of
carbotelluroates. In addition, we compared their proper-
ties with those of carbothioates and carboselenoates.
Organometallic compounds with bonds between the
heavier group 14 elements, such as Ge, Sn, and Pb, and
tellurium have attracted considerable interest due to
their potential as single-source precursors in electronics-
related applications.1,2 Several organometallic com-
pounds containing Ge-Te,3,4 Sn-Te,2,4-9 and Pb-Te
(1) (a) Strauss, A. J . In Concise Encyclopedia of Semiconducting
Materials and Related Technologies; Mahajan, S., Kimerling, L. C.,
Eds.; Pergamon: New York, 1992; p 472. (b) George, J .; Palson, T. I.
Thin Solid Films 1985, 127, 233-239.
(2) (a) Seligson, A. L.; Arnold, J . J . Am. Chem. Soc. 1993, 115, 8214-
8220. (b) Boudjouk, P.; Seidler, D. J .; Bahr, S. R.; McCarthy, G. J .
Chem. Mater. 1994, 6, 2108-2112. (c) Remington, M. P., J r.; Grier, D.
G.; Triebold, W.; J arabek, B. R. Organometallics 1999, 18, 4534-4537.
(3) For acyclic compounds: (a) Tsumuraya, T.; Kabe, Y.; Ando, W.
J . Chem. Soc., Chem. Commun. 1990, 1159-1160. (b) Veith, M.; Stahl,
L.; Huch, V. Z. Anorg. Allg. Chem. 1994, 620, 1264-1270. (c) Hitchcock,
P. B.; J ang, E.; Lappert, M. F. J . Chem. Soc., Dalton Trans. 1995,
3179-3187.
(4) Gardner, S. A.; Trotter, P. J .; Gysling, H. J . J . Organomet. Chem.
1981, 212, 35-42.
Resu lts a n d Discu ssion
(5) For acyclic compounds, see: (a) Einstein, F. W. B.; J ones, C. H.
W.; Sharma, R. D. Can. J . Chem. 1983, 61, 2611-2615. (b) Batchelor,
R. J .; Einstein, F. W. B.; J ones, C. H. W.; Sharma, R. D. Inorg. Chem.
1988, 27, 4636-4640. For cyclic compounds, see: (c) Blecher, A.;
Dra¨ger, M. Angew. Chem., Int. Ed. Engl. 1979, 18, 677. (d) Puff, H.;
Bongartz, A.; Schuh, W.; Zimmer, R. J . Organomet. Chem. 1983, 248,
61-72. (e) Puff, H.; Breuer, B.; Schuh, W.; Sievers, R.; Zimmer, R. J .
Organomet. Chem. 1987, 332, 279-288.
Syn th esis. Group 14 element derivatives of carbo-
telluroates, RCOTeMPh3 (M ) Ge, Sn, Pb), were ob-
(10) Te-alkyl and Te-aryl carbotelluroates are synthesized by react-
ing the corresponding tellurolates with acyl chlorides, but this type of
reaction was inapplicable to the synthesis of heavier group 14 element
derivatives of carbotelluroates because of the difficulty of generating
the RMTe-A+ species (M ) Ge, Sn, Pb; A ) alkali metal). See: (a)
Piette, J . L.; Renson, M. Bull. Soc. Chem. Belg. 1970, 79, 383-390. (b)
Piette, J . L.; Debergh, D.; Baiwir, M.; Llabses, G. Spectrochim. Acta
1980, 36A, 769-773.
(11) Kato, S.; Niyomura, O.; Nakaiida, S.; Kawahara, Y.; Kanda,
T.; Yamada, R.; Hori, S. Inorg. Chem. 1999, 38, 519-530.
(12) (a) Ishihara, H.; Muto, S.; Endo, T.; Komada, M.; Kato, S.
Synthesis 1989, 929-932. (b) Kato, S.; Ishihara, H.; Ibi, K.; Kageyama,
H.; Murai, T. J . Organomet. Chem. 1990, 386, 313-320. (c) Kato, S.;
Ibi, K.; Kageyama, H.; Ishihara, H.; Murai, T. Z. Naturforsch. 1992,
47b, 558-562. (d) Kageyama, H.; Kido, K.; Kato, S.; Murai, T. J . Chem.
Soc., Perkin Trans. 1 1994, 1083-1088.
(6) (a) Schafer, A.; Weidenbruch, M.; Saak, W.; Pohl, S.; Marsmann,
H. Angew. Chem., Int. Ed. Engl. 1991, 30, 834-836. (b) Fischer, J .
M.; Piers, W. E.; Pearce Batchilder, S. D.; Zaworotko, M. J . J . Am.
Chem. Soc. 1996, 118, 283-284. (c) Han, L.-B.; Shimada, S.; Tanaka,
M. J . Am. Chem. Soc. 1997, 119, 8133-8134. (d) J anzen, M. C.;
J enkins, H. A.; Rendina, L. M.; Vittal, J . J .; Puddephatt, R. J . Inorg.
Chem. 1999, 38, 2123-2130.
(7) J ones, C. H. W.; Sharma, R. D.; Taneja, S. P. Can. J . Chem. 1986,
64, 980-986.
(8) Han, L.-B.; Mirzaei, F.; Tanaka, M. Organometallics 2000, 19,
722-724.
(9) Schumann, H.; Thom, K. F.; Schmidt, M. J . Organomet. Chem.
1965, 4, 28-33.
10.1021/om010934b CCC: $22.00 © 2002 American Chemical Society
Publication on Web 02/26/2002

1488 Organometallics, Vol. 21, No. 7, 2002
Tani et al.
Ta ble 1. Syn th esis of Gr ou p 14 Elem en t
Der iva tives of Ca r botellu r oa tes 2-4
Ta ble 3. Sp ectr oscop ic Da ta for
4-CH3C6H4COEMP h 3
R
M
compd
% yielda
M
compd
E
IR ν(CdO)a (cm-1
)
13C NMRb δ(CdO)
1-adamantyl
4-CH3C6H4
4-ClC6H4
1-adamantyl
4-CH3C6H4
4-ClC6H4
1-adamantyl
4-CH3C6H4
4-ClC6H4
Ge
Ge
Ge
Sn
Sn
Sn
Pb
Pb
Pb
2a
2b
2c
3a
3b
3c
4a
4b
4c
15
62
39
25
41
55
39
61
40
Ge
Sc
1651
1654
1676
1621
1644
1654
1618
1641
1655
191.7
192.2
190.0
196.0
194.9
189.8
196.4
195.4
189.8
6
2b
Sed
Te
Sc
Sn
Pb
7
3b
See
Te
Scc
Sef
Te
8
4b
a
a
b
d
Isolated yields.
As KBr disk. In CDCl3. c Reference 14. Reference 12c.
e Reference 12a. f Reference 12b.
Ta ble 2. Sp ectr oscop ic Da ta for Gr ou p 14 Elem en t
Der iva tives of Ca r botellu r oa tes 2-4
RCOTeMe (5),11 whereas those in the Sn and Pb
derivatives 3 and 4 show wavenumbers that are lower
by 10-40 cm-1. In 13C NMR spectra, the signals due to
the carbonyl carbon atom were observed at higher fields
(by 5 ppm) compared to those of the Te-methyl carbo-
telluroates RCOTeMe (5). The Te signals in the 125Te
NMR spectra of carbotelluroates 2-4 are at higher fields
(by 200 ppm) than those of Te-methyl carbotelluroates
RCOTeMe (5) and at lower fields than those of Ph3-
MTePh and (Ph3M)2Te.13 The coupling constants be-
tween the Sn or Pb and Te atoms are 500 and 700 Hz,
which are smaller than those for the MIV-Te single
bonds in Ph3MTePh and (Ph3M)2Te (M ) Sn, ca. 3200
Hz; M ) Pb, ca. 4000 Hz).7,8 These results imply that
the Sn-Te and Pb-Te bonds in 3 and 4 are weaker than
those in Ph3MTePh and (Ph3M)2Te.
compd IR ν(CdO)a (cm-1
)
13C NMRb δ(CdO) 125Te NMRb
δ
2a
2b
2c
3a
3b
3c
4a
4b
4c
1701
1676
1670
1693
1654
1652
1692
1655
1654
207.4
190.0
189.4
207.4
189.8
189.2
207.1
189.8
189.3
276.7
350.2
370.4
204.5
288.2
304.8
338.2
409.4
420.6
a
b
As KBr disk. In CDCl3.
tained by reacting sodium carbotelluroates 1 with
Ph3MCl (eq 1, Table 1). For example, to a degassed Et2O
Some of the IR and 13C NMR spectroscopic data of
group 14 element derivatives of carbochalcogenoates are
given in Table 3. The CdO stretching absorption shifted
to a higher frequency upon going from S to Se and Te.
The signals due to the carbonyl carbon atoms in the 13C
NMR spectra also shifted to higher fields in the same
order, except for Ge derivatives. These results suggest
that the CdO bonds in Te derivatives may be stronger
than those in S and Se derivatives. This tendency may
depend on the degree of intramolecular coordination of
the oxygen atom with the group 14 elements.
X-r a y Cr ysta llogr a p h y. Suitable crystals for X-ray
analysis were obtained by the recrystallization of 2b,
3b, and 4b from mixed solvents of Et2O/CH2Cl2/hexane,
Et2O/hexane, and Et2O/AcOEt/hexane at -20 °C, re-
spectively. Although the crystals of these compounds are
not isomorphous, their forms are quite similar and
resemble that of the corresponding sulfur homologue
4-CH3C6H4COSPbPh3.14 The structure of 4b is shown
in Figure 1, and some important structural data are
listed in Table 4.
This is the first X-ray molecular structure analysis
of compounds bearing a PbIV-Te bond.15 The lengths
of the C(11)-O(11) and C(11)-Te(11) bonds in RCOTe-
MPh3 (M ) Ge, Sn, Pb) are comparable to those in Te-
methyl carbotelluroate,11 diacyl telluride,16a carbotel-
luroato platinum complex,16b and diacyl ditelluride,16c
indicating the existence of CdO double and C-Te single
bonds, respectively. The average sums of the bond
angles around group 14 elements are all 328°, which is
suspension of the sodium salts 1 was added Ph3GeCl
(0.94-1.00 equiv) at 0 °C. The mixture changed from
yellow to pale yellow, together with the precipitation of
a small amount of black tellurium. After the mixture
was stirred at the same temperature for 1-3 h, the
resulting insoluble parts (black tellurium and NaCl)
were filtered in vacuo. The solution was concentrated
to half its original volume, and filtration of the resulting
precipitates gave the corresponding Te-germyl carbo-
telluroates 2 as pale yellow microfine crystals in isolated
yields of 15-62%. Under similar conditions, the reaction
of 1 with Ph3SnCl and Ph3PbCl gave the corresponding
Te-stannyl and Te-plumbyl carbotelluroates 3 and 4 as
colorless and pale yellow microfine crystals in isolated
yields of 25-55% and 39-61%, respectively. Compounds
2-4 are more stable than Te-alkyl carbotelluroates. No
liberation of black tellurium was observed, even when
2-4 were exposed to the air for at least 1 day. On the
other hand, when compounds 2-4 were dissolved in a
solvent such as CH2Cl2 or CHCl3, black tellurium was
liberated even at -20 °C, leading to a complex mixture
containing (Ph3M)2Te (M ) Ge,7 Sn,8 Pb8) within 6 h.
This instability of 2-4 in solution is in marked contrast
to the stability of group 14 element derivatives of
carboselenoates.12
(13) The 125Te signals are as follows. Ph3MTePh: M ) Ge, -11.0
ppm; M ) Sn, -205.8 ppm; M ) Pb, -50.7 ppm.4 (Ph3M)2Te: M ) Ge,
-832 ppm; M ) Sn, -1290 ppm; M ) Pb, -1079 ppm.7,8
(14) Tani, K.; Kanda, T.; Kato, S.; Inagaki, S. Org. Lett. 2001, 3,
655-657.
Spectroscopic data for group 14 element derivatives
of carbotelluroates 2-4 are shown in Table 2. The ν(Cd
O) bands in Ge derivatives 2 are nearly the same as
those of the corresponding Te-methyl carbotelluroates

Group 14 Element Derivatives of Carbotelluroates
Organometallics, Vol. 21, No. 7, 2002 1489
F igu r e 1. ORTEP drawing of 4-CH3C6H4COTePbPh3 (4b).
Hydrogen atoms have been omitted for clarity.
F igu r e 2. ORTEP drawing of 4-CH3C6H4COSePbPh3 (8).
Hydrogen atoms have been omitted for clarity.
Ta ble 4. Bon d Len gth s (Å) a n d An gles (d eg) of
Ta ble 5. Bon d Len gth s (Å) a n d An gles (d eg) of
Gr ou p 14 Elem en t Der iva tives 2b-4b
4-CH3C6H4COSeMP h 3 (M ) Ge, Sn , P b)
2b
3b
4b
6
7
8
M(1)‚‚‚O(11)
M(1)-Te(11)
Te(11)-C(11)
O(11)-C(11)
M(1)-C(21)
M(1)-C(31)
M(1)-C(41)
3.332(2)
2.5742(3)
2.181(3)
1.204(3)
1.944(2)
1.951(3)
1.945(3)
3.093(6)
2.745(1)
2.189(9)
1.19(1)
2.147(9)
2.131(8)
2.140(8)
3.159(9)
2.815(1)
2.18(1)
1.22(1)
2.22(1)
2.20(1)
2.24(1)
M(1)‚‚‚O(11)
M(1)-Se(11)
Se(11)-C(11)
O(11)-C(11)
M(1)-C(21)
M(1)-C(31)
M(1)-C(41)
3.131(2)
2.3760(4)
1.953(3)
1.210(3)
1.944(3)
1.944(3)
1.942(2)
3.068(4)
2.5515(7)
1.934(5)
1.199(6)
2.121(5)
2.145(5)
2.128(5)
3.130(4)
2.6365(5)
1.941(4)
1.205(6)
2.198(4)
2.209(4)
2.202(4)
M(1)-Te(11)-C(11)
O(11)‚‚‚M(1)-C(31)
93.76(7)
158.28(8)
86.5(2)
166.5(3)
87.5(3)
166.5(4)
M(1)-Te(11)-C(11)
O(11)‚‚‚M(1)-C(31)
96.33(8)
157.04(8)
92.4(2)
156.5(2)
92.6(1)
154.5(1)
ORTEP drawing of 8 is shown in Figure 2. Selected bond
distances and angles are listed in Table 5.
similar to the ideal tetrahedral value. The Ge(1)-Te-
(11) and Sn(1)-Te(11) bond distances are also close to
those of cyclic and noncyclic compounds with Ge-Te3
and Sn-Te single bonds.5 The Pb(1)-Te(11) bond
distance (2.815(1) Å) is in good agreement with the sum
of the tellurium covalent radius (1.32 Å)17 and the Pb-
(IV) metallic radius (1.50 Å),18 which suggests a single
bond between Pb(IV) and Te.
In 2b, 3b, and 4b, the M‚‚‚O (M ) Ge, Sn, Pb)
distances are shorter than the sum of the van der Waals
radii of both atoms,17 which suggests that a nonbonding
intramolecular interaction is present between the non-
bonding orbital on the carbonyl oxygen atom (nO) and
the σ*MC31 orbital ( O(11)‚‚‚M(1)-C(31) ) 160°) and/
or the σ*MTe orbital, similar to the case for the corre-
sponding carbothioate derivatives.14 Interestingly, even
though the atomic radius of Sn is greater than that of
Ge, the CdO‚‚‚Sn distance in 3b is shorter than the Cd
O‚‚‚Ge distance in 2b by about 0.1 Å.
The molecular forms are comparable to those of the
carbotelluroate derivatives and carbothioate deriva-
tives.14 The C-O, C-Se, and Se-M (M ) Ge, Sn, Pb)
bond lengths of the carboselenoate derivatives show Cd
O double and C-Se and Se-M single bonds, respec-
tively.18,19 As expected, the distances between the
carbonyl oxygen and the central group 14 elements are
significantly shorter than the sum of the van der Waals
radii of both atoms,17 and the CdO‚‚‚Sn distance in 7
is about 0.1 Å shorter than the CdO‚‚‚Ge distance in 6,
similar to the case of carbotelluroates 2b and 3b.
Ca lcu la tion . To explain the unusual shortening of
the CdO‚‚‚Sn distance, which is probably caused by
nonbonding intramolecular interaction, ab initio MO
calculations at the B3LYP/LANL2DZ+p level20 were
performed with the Gaussian 98 program21 on the model
compounds trimethylgermyl, trimethylstannyl, and tri-
methylplumbyl ethanechalcogenoates, CH3COEM(CH3)3
(E ) Se, M ) Ge (9), Sn (10), Pb (11); E ) Te: M ) Ge
(12), Sn (13), Pb (14)). Selected bond distances and
angles are listed in Table 6.
For comparison, an X-ray structural analysis of the
selenium homologues, i.e., 4-CH3C6H4COSeMPh3 (6, M
) Ge; 7, M ) Sn; 8, M ) Pb), was carried out. An
The M‚‚‚O distances in the optimized structures for
carboselenoates and carbotelluroates were similar to
those obtained by X-ray analysis; i.e., the Ge‚‚‚O dis-
tances are longer than those with Sn and Pb. To obtain
further information regarding the electronic structures,
NBO (natural bond orbital) analyses were carried out.21
(15) X-ray molecular structural analyses of PbTe compounds have
not been performed, except for PbII-Te species. For the dilead
tritelluride anion, Pb2Te32-, see: (a) Bjo¨rgvinsson, M.; Sawyer, J . F.;
Schrobilgen, G. J . Inorg. Chem. 1991, 30, 2231-2233. (b) Bjo¨rgvinsson,
M.; Mercier, H. P. A.; Mitchell, K. M.; Schrobilgen, G. J .; Strohe, G.
Inorg. Chem. 1993, 32, 6046-6055. (c) Park, C.-W.; Salm, R. J .; Ibers,
J . A. Can. J . Chem. 1995, 73, 1148-1156. (d) J ones, C. D. W.; DiSalvo,
F. J .; Haushalter, R. C. Inorg. Chem. 1998, 37, 821-823. (e) Borrmann,
H.; Campbell, J .; Dixon, D. A.; Mercier, H. P. A.; Pirani, A. M.;
Schrobilgen, G. J . Inorg. Chem. 1998, 37, 6656-6674. For [(Me3-
Si)3SiTe]2Pb, see: (f) Seligson, A. L.; Arnold, J . J . Am. Chem. Soc. 1993,
115, 8214-8220.
2
(19) Csp dO ) 1.20-1.23 Å: Allen, F. H.; Kennanl, O.; Watson, D.
G.; Brammer, L.; Orpen, A. G.; Taylor, R. J . Chem. Soc., Perkin Trans.
2 1987, S1-S19.
(16) (a) Sewing, D.; du Mont, W.-W.; Pohl, S.; Saak, W.; Lenoir, D.
Z. Anorg. Allg. Chem. 1998, 624, 1363-1368. (b) Kato, S.; Niyomura,
O.; Kawahara, Y.; Kanda, T. J . Chem. Soc., Dalton Trans. 1999, 1677-
1685. (c) Niyomura, O.; Kato, S.; Inagaki, S. J . Am. Chem. Soc. 2000,
122, 2132-2133.
(20) The Becke-style three-parameter density functional theory
using the Lee-Yang-Parr correlation functional (B3LYP) was applied
in our calculations. The effective core potentials (ECPs) LANL2DZ+p
were used for C, O, Se, Te, Ge, Sn, and Pb. The d polarization function
for the ECP basis set of all atoms, except for H, are taken from:
Huzinaga, S.; Andzelm, J .; Klobukowski, M.; Radzio-Andzelm, Y.;
Sakai, Y.; Tatewaki, H. Gaussian Basis Sets for Molecular Calculations;
Elsevier: Amsterdam, 1984.
(17) Bondi, A. J . Phys. Chem. 1964, 68, 441-451.
(18) Pauling, L. The Chemical Bond; Cornell University Press:
Ithaca, NY, 1976; pp 135-220.

1490 Organometallics, Vol. 21, No. 7, 2002
Tani et al.
Ta ble 6. Ca lcu la ted Geom etr ica l P a r a m eter s
(Bon d Dista n ces in Å a n d An gles in d eg) for
CH3COEM(CH3)3 (E ) Se, Te; M ) Ge, Sn , P b) a t
th e B3LYP /LANL2DZ+p Level
Ta ble 8. NBO An a lysis (∆Ea in k ca l m ol-1) of
CH3COEM(CH3)3 (E ) Se, Te; M ) Ge, Sn , P b) a t
th e B3LYP /LANL2DZ+p Level
CH3COSeM(CH3)3
M ) Ge (9)
M ) Sn (10)
M ) Pb (11)
M(1)‚‚‚O(3)
M(1)-Se(2)
Se(2)-C(4)
O(3)-C(4)
M(1)-C(6)
M(1)-C(7)
M(1)-C(8)
3.254
2.442
1.214
1.967
1.967
1.973
1.967
3.203
2.616
1.216
1.963
2.142
2.149
2.142
3.235
2.681
1.217
1.959
2.198
2.208
2.198
CH3COSeM(CH3)3
M ) Ge (9)
M ) Sn (10)
M ) Pb (11)
nO f σ*MSe
nO f σ*MC(7)
1.33
1.88
1.23
1.98
M(1)-Se(2)-C(4)
96.89
93.65
93.45
1.55
CH3COTeM(CH3)3
CH3COTeM(CH3)3
M ) Ge (12) M ) Sn (13) M ) Pb (14)
M ) Ge (12)
M ) Sn (13)
M ) Pb (14)
M(1)‚‚‚O(3)
M(1)-Te(2)
Te(2)-C(4)
O(3)-C(4)
M(1)-C(6)
M(1)-C(7)
M(1)-C(8)
3.409
2.638
1.212
2.185
1.970
1.076
1.970
3.332
2.808
1.214
2.183
2.145
2.151
2.145
3.348
2.863
1.214
2.181
2.203
2.211
2.203
nO f σ*MTe
nO f σ*MC(7)
1.08
1.54
1.71
a
∆E ) stabilization energies associated with delocalization.
related to the unusual shortening of the CdO‚‚‚Sn
distances. In fact, NBO analysis suggested that two
types of nonbonding orbital interactions (nOfσ*ME and
nOfσ*MC7) contribute to the shortening, as shown in
Table 8. In carboselenoates, both interactions are equally
important, whereas nOfσ*MC7 plays a dominant role in
carbotelluroates. This is in sharp contrast to the case
of carbothioates, in which nOfσ*MS is more important.
M(1)-Te(2)-C(4)
93.56
89.86
89.49
Ta ble 7. Or bita l En er gy a n d Con tr ibu tion s of
Atom ic Or bita ls for CH3COEM(CH3)3 (E ) Se, Te;
M ) Ge, Sn , P b) a t th e B3LYP /LANL2DZ+p Level
CH3COSeM(CH3)3
M ) Ge (9) M ) Sn (11) M ) Pb (11)
orbital energy (au)
Con clu sion
nO(1)a
nO(2)b
σ*MSe
σ*MC7
σ*MSe (%)
M
-0.67480
-0.27414
0.10997
-0.67742
-0.27631
0.07814
-0.67336
-0.27205
0.05593
We have described the synthesis and molecular and
electronic structures of the first group 14 element
derivatives of carbotelluroates. They were synthesized
as stable compounds in low to good yields. X-ray
molecular analysis and theoretical calculations revealed
an unusual shortening of the CdO‚‚‚Sn distances and
nonbonding intramolecular interactions between the
oxygen and Sn atoms. NBO analysis indicated that this
0.26792
0.19951
0.14229
70.36
29.64
74.88
25.12
74.96
25.06
Se
σ*MC7 (%)
M
C7
72.49
27.51
75.70
24.30
73.31
26.69
CH3COTeM(CH3)3
is predominantly due to nOfσ*MC7
.
M ) Ge (12) M ) Sn (13) M ) Pb (14)
Exp er im en ta l Section
orbital energy (au)
nO(1)a
nO(2)b
σ*MTe
σ*MC7
σ*MTe (%)
M
-0.67637
-0.28023
0.08469
-0.67909
-0.28221
0.06247
-0.67650
-0.27957
0.04650
Reactions were carried out under argon using standard
Schlenk techniques. Sodium carbotelluroates11 were prepared
as described in the literature. Ph3GeCl, Ph3SnCl, and Ph3PbCl
were used as purchased from Aldrich Chemical Co. All solvents
were purified under argon and dried as indicated: Et2O and
hexane were refluxed with sodium benzophenone ketyl and
distilled before use. CH2Cl2 and AcOEt were distilled over
diphosphorus pentaoxide after refluxing for 5 h. All solvents
were degassed before use. 1H (399.7 MHz) and 13C NMR (100.4
0.25843
0.19099
0.13618
64.52
35.48
69.88
30.12
70.05
29.95
Te
σ*MC7 (%)
M
72.23
27.77
75.52
24.48
73.19
26.81
C7
a
b
The sp0.7 hybridized lone pair of the carbonyl oxygen. The
p-type lone pair of the carbonyl oxygen.
(21) (a) Frisch, M. J .; Trucks, G. W.; Schlegel, H. B.; Scuseria, G.
E.; Robb, M. A.; Cheeseman, J . R.; Zakrzewski, V. G.; Montgomery, J .
A., J r.; Stratmann, R. E.; Burant, J . C.; Dapprich, S.; Millam, J . M.;
Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J .;
Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo,
C.; Clifford, S.; Ochterski, J .; Petersson, G. A.; Ayala, P. Y.; Cui, Q.;
Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.;
Foresman, J . B.; Cioslowski, J .; Ortiz, J . V.; Stefanov, B. B.; Liu, G.;
Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.;
Fox, D. J .; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.;
Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; J ohnson, B. G.; Chen,
W.; Wong, M. W.; Andres, J . L.; Head-Gordon, M.; Replogle, E. S.;
Pople, J . A. Gaussian 98; Gaussian, Inc.: Pittsburgh, PA, 1998. (b)
Foster, J . P.; Weinhold, F. J . Am. Chem. Soc. 1980, 102, 7211-7218.
(c) Carpenter, J . E.; Weinhold, F. J . Am. Chem. Soc. 1988, 110, 368-
372. (d) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88,
899-926.
The results regarding orbital energies and the magni-
tude of the contribution of atomic orbitals to σ*ME and
σ*MC7 are listed in Table 7, and the stabilization
energies are listed in Table 8.
The orbital energy of σ*GeE (E ) Se, Te) is higher than
that of σ*ME (M ) Sn, Pb; E ) Se, Te). The σ*GeC and
σ*GeE orbitals extend to the carbon and chalcogen atoms
more deeply than those in the corresponding Sn and Pb
derivatives. These tendencies were also observed for
carbothioate derivatives. However, these orbital ener-
gies and atomic orbital contributions are not directly

Group 14 Element Derivatives of Carbotelluroates
Organometallics, Vol. 21, No. 7, 2002 1491
Ta ble 9. Cr ysta llogr a p h ic Da ta
2b
3b
4b
6
7
8
formula
fw
color
cryst size (mm)
C
26H22OGeTe
C26H22OSnTe
596.75
pale yellow
0.43 × 0.40 ×
0.29
C26H22OPbTe
685.26
pale yellow
0.26 × 0.14 ×
0.11
C26H22OGeSe
502.01
colorless
0.23 × 0.43 ×
0.43
C26H22OSnSe
548.11
colorless
0.23 × 0.23 ×
0.29
C26H22OPbSe
636.62
yellow
550.65
yellow
0.14 × 0.23 ×
0.23 × 0.31 ×
0.34
0.34
T (K)
193
193
193
193
296
193
cryst syst
space group
a (Å)
b (Å)
c (Å)
triclinic
P1h
monoclinic
P21/c
13.680(4)
9.625(2)
18.774(2)
monoclinic
P21/c
13.703(2)
9.671(1)
18.865(1)
triclinic
P1h
triclinic
P1h
triclinic
P1h
9.376(1)
16.058(3)
8.061(1)
93.04(2)
110.39(1)
92.10(1)
1134.1(3)
2
9.3795(9)
16.058(1)
7.9443(7)
91.582(7)
111.759(7)
93.821(7)
1107.1(2)
2
9.592(1)
16.309(2)
7.8722(6)
92.497(8)
109.783(6)
91.956(10)
1156.1(2)
2
9.618(1)
16.052(3)
7.811(1)
92.83(2)
109.32(1)
91.36(1)
1135.6(3)
2
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
110.72(1)
110.972(7)
2312.0(9)
4
1.714
2334.5(5)
4
1.950
Dcalcd (g cm-3
)
1.612
2.625
1.506
3.041
504.00
5406/5092
3867
0.027, 0.085
1.00
0.52, -0.54
1.574
2.693
540.00
5619/5302
3692
0.048, 0.120
1.17
1.18, -1.30
1.862
9.057
604.00
5406/5217
4449
0.025, 0.073
0.96
0.83, -1.16
µ (mm-1
F(000)
)
2.356
8.478
540.00
5527/5210
4326
0.024, 0.077
1.00
1152.00
5874/5323
3565
0.032, 0.179
1.88
1280.00
5929/5375
2561
0.045, 0.136
0.98
no. of rflns: measd/unique
no. of observns (I > 2σ(I))
R1, wR2
goodness of fit
final max, min ∆F (e Å-3
)
0.59, 0.36
1.07, -0.97
2.80, -5.78
MHz) were recorded using CDCl3 as a solvent with Me4Si as
myl 1-adamantanecarbotelluroate 2a is described in detail as
a typical procedure for compounds 2-4.
1
an internal standard for H NMR and CDCl3 for 13C NMR with
a J EOL J NM-R400 spectrometer. In 119Sn NMR spectra (126.0
MHz), Me4Sn was used as an external standard. In 125Te NMR
spectra (149.0 MHz), Me2Te was used as an external standard.
IR spectra were measured on a Perkin-Elmer FT-IR 1640
spectrophotometer. Elemental analyses were performed at the
Elemental Analysis Center of Kyoto University.
Te-Tr iph en ylger m yl 1-Adam an tan ecar botellu r oate (2a).
Ph3GeCl (0.385 g, 1.13 mmol) was added to a suspension of
sodium 1-adamantanecarbotelluroate (0.356 g, 1.13 mmol) in
Et2O (10 mL) at 0 °C under an argon atmosphere. The mixture
rapidly changed from yellow to pale yellow together with the
precipitation of a small amount of black tellurium. After the
mixture was stirred at the same temperature for 1.5 h, the
insoluble parts (black tellurium and NaCl) were filtered off
by a glass filter (G4) in vacuo. Hexane (7 mL) was added to
the filtrate, and the solution was concentrated to ca. 15 mL
under reduced pressure (0 °C, 26.7 Pa). Filtration of the
resulting precipitates gave 0.104 g (15%) of 2a as colorless
X-r a y Cr ysta llogr a p h y. Crystal samples were cut from
grown crystals and mounted on a glass fiber. The crystals were
coated with an epoxy resin because they were sensitive to air.
Measurements were carried out on a Rigaku AFC7R four-circle
diffractometer using a graphite monochromator with Mo KR
radiation (λ ) 0.710 69 Å). The data were collected at 193 or
296 K. The cell dimensions were determined from a least-
squares refinement of the setting diffractometer angles for 25
automatically centered reflections. The intensities of 3 repre-
sentative reflections were measured after every 150 reflections.
The structure was solved by a direct method using SHELXS8622
and expanded using DIRDIF94.23 An empirical absorption
correction (ψ-scan) was also applied. Neutral atom scattering
factors for neutral atoms were from Cromer and Waber,24 and
anomalous dispersion effects25 were used. The function mini-
mized was ∑w(Fo2 - Fc2)2, and the weighting scheme was w )
1/[σ2(Fo2)]. Full-matrix least-squares refinement was executed,
with non-hydrogen atoms being anisotropic. The final least-
squares cycle included fixed hydrogen atoms at calculated
positions for which each isotropic thermal parameter was set
to 1.2 times that of the connecting atoms. All calculations were
performed using the teXsan crystallographic software package
of Molecular Structure Corp. Crystallographic data of 2b-4b
and 6-8 are summarized in Table 9.
microfine crystals. Mp: 99-104 °C dec. Anal. Calcd for C29H30
-
OGeTe: C, 58.57; H, 5.08. Found: C, 58.28; H, 5.00. IR (KBr,
1
cm-1): 1701 ν(CdO). H NMR (CDCl3): δ 1.56 (m, 6 H, Ad),
1.68 (d, 6 H, J ) 2.7 Hz, Ad), 1.94 (s, 3 H, Ad), 7.17-7.29 (m,
9 H, Ar), 7.51-7.54 (m, 6 H, Ar). 13C NMR (CDCl3): δ 28.2,
36.5, 39.2, 56.1, 128.3, 129.4, 135.0, 136.2, 207.4 (CdO). 125Te
NMR (CDCl3): δ 276.7.
Te-Tr ip h en ylger m yl 4-Meth ylben zen eca r botellu r oa te
(2b). The compound was obtained as pale yellow microfine
crystals (62%). Mp: 117-118 °C dec. Anal. Calcd for C26H22
-
OGeTe: C, 56.71; H, 4.03. Found: C, 56.69; H, 4.02. IR (KBr,
1
cm-1): 1676 ν(CdO). H NMR (CDCl3): δ 2.22 (s, 3 H, CH3),
7.05 (d, 2 H, J ) 8.5 Hz, Ar), 7.26-7.29 (m, 9 H, Ar), 7.54-
7.59 (m, 8 H, Ar). 13C NMR (CDCl3): δ 21.6 (CΗ3), 128.4, 129.3,
129.6, 134.1, 135.0, 135.8, 140.7, 144.8, 190.0 (CdO). 125Te
NMR (CDCl3): δ 350.2.
Te-Tr ip h en ylger m yl 4-Ch lor oben zen eca r botellu r oa te
(2c). The compound was obtained as pale yellow microfine
Syn th esis of Te-Tr ip h en yl Gr ou p 14 Elem en t Der iva -
tives of Ca r botellu r oa tes. The synthesis of Te-triphenylger-
crystals (39%). Mp: 105-107 °C dec. Anal. Calcd for C25H19
-
OClGeTe: C, 52.58; H, 3.35. Found: C, 52.28; H, 3.54. IR (KBr,
cm-1): 1670 ν(CdO). 1H NMR (CDCl3): δ 7.18 (d, 2 H, J ) 8.8
Hz, Ar), 7.25-7.27 (m, 9 H, Ar), 7.54-7.57 (m, 6 H, Ar), 7.57
(d, 2 H, J ) 8.8 Hz, Ar). 13C NMR (CDCl3): δ 128.5, 128.8,
129.4, 129.7, 134.7, 135.5, 140.2, 141.5, 189.4 (CdO). 125Te
NMR (CDCl3): δ 370.4.
(22) Sheldrick, G. M. In Crystallographic Computing 3; Sheldrick,
G. M., Kruger, C., Goddard, R., Eds.; Oxford University Press: New
York, 1985; pp 175-189.
(23) The DIRDIF94 program system was used: Beukskens, P. T.;
Admiraal, G.; Beurskiens, G.; Bosman, W. P.; de Gelder, R.; Israel,
R.; Smits, J . M. M. DIRDIF94; Technical Report of the Crystallography
Laboratory; University of Nijmegen, Nijmegen, The Netherlands, 1994.
(24) Cromer, D. T.; Waber, J . T. International Tables for X-ray
Crystallography; Ibers, J . A., Hamilton, W. C., Eds.; Kynoch Press:
Birmingham, England, 1974; Vol. IV, Table 2.2A.
Te-Tr ip h en ylst a n n yl 1-Ad a m a n t a n eca r b ot ellu r oa t e
(3a ). The compound was obtained as colorless microfine
crystals (25%). Mp: 99-104 °C dec. Anal. Calcd for C29H30
-
OSnTe: C, 54.35; H, 4.72. Found: C, 54.47; H, 4.84. IR (KBr,
(25) Creagh, D. C.; McAuley, W. J . International Tables for X-ray
Crystallography; Wilson, A. J . C., Ed.; Kluwer Academic: Boston, MA,
1992; Vol. C, Table 4.2.6.8, pp 219-222.
1
cm-1): 1693 ν(CdO). H NMR (CDCl3): δ 1.55 (m, 6 H, Ad),
1.67 (d, 6 H, J ) 2.7 Hz, Ad), 1.93 (s, 3 H, Ad), 7.24-7.29 (m,

1492 Organometallics, Vol. 21, No. 7, 2002
Tani et al.
9 H, Ar), 7.48-7.61 (m, 6 H, Ar). 13C NMR (CDCl3): δ 28.2,
Te-Tr iph en ylplu m byl 4-Meth ylben zen ecar botellu r oate
(4b). The compound was obtained as pale yellow microfine
1
13
117
36.4, 39.5, 56.4, 128.6, 129.3, 136.8, 137.9 ( J
) 494
C- Sn
1
Hz, J
-136.3 ( J
) 518 Hz), 207.4 (CdO). 119Sn NMR (CDCl3): δ
13
119
C- Sn
crystals (61%). Mp: 111-112 °C dec. Anal. Calcd for C26H22
-
1
1
C ) 518 Hz, J
Te ) 2792 Hz). 125Te NMR
1
125
119
13
119
125
Sn-
Sn-
OPbTe: C, 45.57; H, 3.24. Found: C, 45.27; H, 3.40. IR (KBr,
cm-1): 1655 ν(CdO). 1H NMR (CDCl3): δ 2.31 (s, 3H, CH3),
7.14 (d, 2 H, J ) 8.2 Hz), 7.29-7.47 (m, 9 H), 7.68 (d, 2 H, J
) 8.2 Hz), 7.71-7.74 (m, 6 H). 13C NMR (CDCl3): δ 21.7 (CH3),
1
125
117
Te- Sn
119
) 2792
Te- Sn
(CDCl3): δ 204.5 ( J
Hz).
) 2670 Hz,
J
Te-Tr ip h en ylsta n n yl 4-Meth ylben zen eca r botellu r oa te
(3b ). The compound was obtained as pale yellow microfine
13
207
128.9, 129.0, 129.3, 129.7, 137.2, 144.1, 144.7, 150.7 (J
C- Pb
crystals (41%). Mp: 117-118 °C dec. Anal. Calcd for C26H22
-
) 431 Hz), 189.8 (CdO). 125Te NMR (CDCl3): δ 409.4 (J
) 3424 Hz).
125
207
Te- Pb
OSnTe: C, 52.33; H, 3.72. Found: C, 52.41; H, 3.79. IR (KBr,
1
cm-1): 1654 ν(CdO). H NMR (CDCl3): δ 2.14 (s, 3 H, CH3),
6.96-7.26 (m, 12 H, Ar), 7.50-7.67 (m, 6 H, Ar). 13C NMR
(CDCl3): δ 21.6 (CΗ3), 128.5, 128.9, 129.4, 136.7, 137.7
Te-Tr ip h en ylp lu m byl 4-ch lor oben zen eca r botellu r oa te
(4c). The compound was obtained as pale yellow microfine
1
1
13
117
C- Sn
13
119
) 523 Hz), 138.0, 139.3, 140.8,
C- Sn
1
119
crystals (40%). Mp: 102-104 °C dec. Anal. Calcd for C25H19
-
( J
) 500 Hz, J
119
13
Sn-
189.8 (CdO). Sn NMR (CDCl3): δ -131.8 ( J
) 523
ClOPbTe: C, 42.55; H, 2.71. Found: C, 42.30; H, 2.66. IR (KBr,
cm-1): 1654 ν(CdO). 1H NMR (CDCl3): δ 7.23-7.27 (m, 5 H),
7.29-7.41 (m, 6 H), 7.62-7.65 (m, 8 H). 13C NMR (CDCl3): δ
C
1
Hz,
J
) 2681 Hz). 125Te NMR (CDCl3): δ 288.2
125
Sn- Te
1
125
119
1
125
117
119
) 2681 Hz).
Te- Sn
( J
) 2560 Hz, J
Te-Tr ip h en ylsta n n yl 4-Ch lor oben zen eca r botellu r oa te
(3c). The compound was obtained as pale yellow microfine
crystals (55%). Mp: 105-107 °C dec. Anal. Calcd for C25H19
Te- Sn
13
207
128.8, 129.0, 129.9, 130.0, 137.2, 140.2, 142.1, 150.7 (J
C- Pb
) 438 Hz), 189.3 (CdO). 125Te NMR (CDCl3): δ 420.6 (J
) 3339 Hz).
125
207
Te- Pb
-
OClSnTe: C, 48.65; H, 3.10. Found: C, 48.74; H, 3.24. IR (KBr,
cm-1): 1652 ν(CdO). 1H NMR (CDCl3): δ 7.23-7.33 (m, 11
H, Ar), 7.54-7.69 (m, 8 H, Ar). 13C NMR (CDCl3): δ 128.6,
Ack n ow led gm en t. This research was supported in
part by a Grant-in-Aid for Scientific Research from the
Ministry of Education, Science, Sports and Culture of
J apan.
1
1
13
117
13
119
) 503 Hz, J
C- Sn
128.8, 129.6, 129.8, 137.1, 137.5 ( J
C- Sn
) 527 Hz), 140.4, 141.6, 189.2 (CdO). 119Sn NMR (CDCl3): δ
1
1
-127.9 ( J
C ) 526 Hz, J
Te ) 2600 Hz). 125Te NMR
1
125
119
13
119
125
Sn-
Sn-
1
125
117
Te- Sn
119
) 2600
Te- Sn
(CDCl3): δ 304.8 ( J
) 2475 Hz,
J
Hz).
Te-Tr ip h en ylp lu m b yl 1-Ad a m a n t a n eca r b ot ellu r oa t e
(4a ). The compound was obtained as pale yellow microfine
Su p p or tin g In for m a tion Ava ila ble: ORTEP drawings
and X-ray crystal data for compounds 2b-4b and 6-8. This
material is available free of charge via the Internet at http://
pubs.acs.org. Crystallographic data for the structural analysis
have been deposited with the Cambridge Crystallographic
Data Centre, CCDC Nos. 178958-178963, for the compounds
2b-4b and 6-8, respectively.
crystals (39%). Mp: 111-114 °C dec. Anal. Calcd for C29H30
-
OPbTe: C, 47.76; H, 4.15. Found: C, 47.78; H, 4.18. IR (KBr,
1
cm-1): 1692 ν(CdO). H NMR (CDCl3): δ 1.55 (m, 6H, CH2),
1.77 (d, 6 H, J ) 2.7 Hz, CH2), 1.92 (s, 3 H, CH), 7.11-7.35
(m, 9 H), 7.56-7.58 (m, 6 H). 13C NMR (CDCl3): δ 28.3, 36.4,
13
207
39.8, 56.5, 128.7, 129.5, 137.1, 150.4 (J
Pb ) 419 Hz), 207.1
C-
125
125
207
(CdO). Te NMR (CDCl3): δ 338.2 (J
) 3561 Hz).
OM010934B
Te- Pb