A Discrete Chlorotellurate [Cl4Te-Mn(CO)5]-: Coordinative Addition of the Metalloanion [Mn(CO)5]- to TeCl4

Full text of DOI:10.1021/ic9708677

Inorg. Chem. 1998, 37, 1131-1134
1131
A Discrete Chlorotellurate [Cl4Te-Mn(CO)5]-:
Scheme 1
Coordinative Addition of the Metalloanion
[Mn(CO)5]- to TeCl4
Wen-Feng Liaw,*,† Show-Jen Chiou,†
Gene-Hsiang Lee,‡ and Shie-Ming Peng§
Department of Chemistry, National Changhua University of
Education, Changhua 50058, Taiwan,
and Instrumentation Center and Department of Chemistry,
National Taiwan University, Taipei 10764, Taiwan
ReceiVed July 9, 1997
Introduction
Scheme 2
The reaction of the chalcogen(IV) halide gives rise to an
extensive chemistry.1 Some known reactions are outlined in
Scheme 1: a degradation to tri-, di-, and mononuclear halotel-
lurate in solution from (TeCl4)4 (Scheme 1a),2 a metathesis
reaction to organochalcogen halides/organochalcogenide (Scheme
lb),3 the formation of [TeCl3][AlCl4] and [PCl4][TeCl5] in the
reaction of TeCl4 with both Lewis acids (AlCl3) and Lewis bases
(PCl5), respectively (Scheme 1c,d),4 the formation of hydronium
halochalcogenates by reaction of chalcogen halides with aqueous
acids (Scheme 1e),1,5 and an oxidative addition to rhodium(I)
compound (Scheme 1f).6
Recent work in our group has shown that oxidative addition
of diorganyl dichalcogenides to coordinatively unsaturated, low-
valent, anionic [Mn(CO)5]- led to the formation of cis-[Mn-
(CO)4(ER)2]- (E ) Se, Te, S; R ) phenyl, alkyl) complexes.10
We report here the reaction of TeCl4 and [Mn(CO)5]-, which
results in the formation of a discrete chlorotellurate [Cl4Te-
Mn(CO)5]-.
Also, synthetic strategies for transition-metal-telluride com-
pounds have been based on TeCl4 as the straightforward
synthesis route (Scheme 1g).7,8 In spite of the large number of
dimeric and trimeric halotellurates known1 and the possible
discrete pentahalotellurate TeCl5- without any secondary bond-
ing interactions proposed,9 we noticed the only example of a
nonassociated mononuclear nonoctahedral chlorotellurate(IV)
of the type XY5E (X ) chalcogen, E ) lone-pair electron) is
limited to tetragonal pyramidal TeCl4(OR)- (R ) H, CH3, C2H5,
C5H9) with the inert pair at Te in the trans position to the OR-
ligand.1,5
Results and Discussion
Although oxidative addition across the Te-Cl bond of TeCl4
to [Mn(CO)5]- (Scheme 2a) or nucleophilic displacement
(Scheme 2b) might be expected to be the preferred process in
the reaction of TeCl4 and [PPN][Mn(CO)5], the failure to
observe these two possible reaction routes in the case of
[Mn(CO)5]- is surprising since the facility of the d8 configu-
ration of [Mn(CO)5]- and [RTeFe(CO)4]- to lose two electrons
(oxidative addition) is well-known.10,11 Contrary to this ex-
pectation, the discrete mononuclear chlorotellurate adduct [Cl4-
Te-Mn(CO)5]- (Scheme 2c) was obtained from reaction of
[PPN][Mn(CO)5] and TeCl4 in THF at -15 °C. The light green
[Cl4Te-Mn(CO)5]- is soluble in common organic solvents, such
as THF, CH3CN, and MeOH, and can be crystallized from vapor
† National Changhua University of Education.
‡ Instrumentation Center, National Taiwan University.
§ Department of Chemistry, National Taiwan University.
(1) (a) Krebs, B.; Ahlers, F.-P. AdV. Inorg. Chem. 1990, 35, 235. (b)
Haiduc, I.; King, R. B.; Newton, M. G. Chem. ReV. 1994, 94, 301.
(c) Chivers, T.; Gao, X.; Parvez, M. Inorg. Chem. 1996, 35, 9.
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McWhinnie, W. R.; Hamor, T. A. J. Chem. Soc., Dalton Trans. 1988,
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(10) (a) Liaw, W.-F.; Ou, D.-S.; Li, Y.-S.; Lee, W.-Z.; Chuang, C.-Y.;
Lee, Y.-P.; Lee, G.-H.; Peng, S.-M. Inorg. Chem. 1995, 34, 3747. (b)
Liaw, W.-F.; Chuang, C.-Y.; Lee, W.-Z.; Lee, C.-K.; Lee, G.-H.; Peng,
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Wang, C.-Y.; Lee, G.-H.; Peng, S.-M. Inorg. Chem. 1997, 36, 1253.
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Chem. 1986, 25, 777. (b) Krebs, B.; Buss, B.; Berger, W. Z. Anorg.
Allg. Chem. 1973, 397, 1.
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Inorg. Chem. 1993, 32, 1536. (b) Liaw, W.-F.; Ou, D.-S.; Horng, Y.-
C.; Lai, C.-H.; Lee, G.-H.; Peng, S.-M. Inorg. Chem. 1994, 33, 2495.
(c) Liaw, W.-F.; Lai, C.-H.; Lee, C.-K.; Lee, G.-H.; Peng, S.-M. J.
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S0020-1669(97)00867-7 CCC: $15.00 © 1998 American Chemical Society
Published on Web 02/18/1998

1132 Inorganic Chemistry, Vol. 37, No. 5, 1998
Notes
diffusion of hexane into concentrated THF solution at -15 °C
under nitrogen. Under an atmosphere of dry N2, significant
decomposition (in the crystal state) occurs at room temperature
due to the diffusion of the solvated THF. Both heat and light
appear to contribute separately to this decomposition. The light
green thin-plate [PPN][Cl4Te-Mn(CO)5] crystals could be stored
for extended periods if kept in hexane at -15 °C under nitrogen.
Following extended periods of stirring in THF at ambient
temperature, a solution of [PPN][Cl4Te-Mn(CO)5] converted into
an orange solution with a precipitate of black Te powder.12 This
transformation, which was also indicated by the appearance of
two new bands for the ν(CO) vibrations in THF (2017 s, 1928
vs cm-1), occurred at ambient temperature, and during this
period, no intermediate was detected spectrally. X-ray analysis
and IR ν(CO) spectra revealed the orange compound to be a
well-known binuclear species of composition [PPN][(CO)3Mn-
(µ-Cl)3Mn(CO)3].12,13 This transformation is in contrast to the
formation of Re(CO)5Cl, [(CO)3Re(µ-Cl)3Re(CO)3]- (ν(CO)
(THF): 2016 s, 1914 vs cm-1), and Te powder for a solution
of the [Cl4Te-Re(CO)5]- being stirred in THF at ambient
temperature. It appears that the [Cl4Te-Mn(CO)5]- is much less
apt to decompose than is [Cl4Te-Re(CO)5]- in THF. The IR
spectral data for [Cl4Te-Mn(CO)5]- exhibit a three-band pattern
in the CO stretching region at 2129 w, 2049 vs, and 2009 m
cm-1 (THF), which is consistent with a pentacarbonyl derivative
of approximately C4V symmetry.14 We also noticed that the
adduct [Cl4Te-Mn(CO)5]- is much more stable in MeOH at
room temperature, which is probably due to the “Mn-Te-
Cl‚‚‚H-OMe and Mn-Te‚‚‚H-OMe” interactions that greatly
retard thermal transformation of [Cl4Te-Mn(CO)5]-. However,
the complete decomposition was also observed when stirring
the [Cl4Te-Mn(CO)5]- MeOH solution at ambient temperature
for 30 min. The presence of these interactions by MeOH in
[Cl4Te-Mn(CO)5]- adduct leads to a shift in the ν(CO) vibra-
tions to higher frequency (2130 w, 2051 vs, 2038 m, 2023 w
cm-l). In a similar fashion, a solution of the unstable [Cl4Se-
Mn(CO)5]- converted into brick-red Se solid and [(CO)3Mn-
(µ-Cl)3Mn(CO)3]- in THF at room temperature. In comparison,
the thermally unstable [Cl4Se-Re(CO)5]- decomposed into Re-
(CO)5Cl, brick-red Se solid, and unidentified compound.
Definitive assignment of the structure of [PPN][Cl4Te-Mn-
(CO)5] was obtained by X-ray crystallography; the structure of
the [Cl4Te-Mn(CO)5]- unit in the PPN+ salt is shown in Figure
1. This compound crystallizes as discrete cations of PPN+,
anions of [Cl4Te-Mn(CO)5]-, and THF solvent; there are no
exceptional cation-anion interactions. The coordination about
Te in [Cl4Te-Mn(CO)5]- can be considered as essentially
tetragonal pyramidal (pseudooctahedral), with the position trans
to the Te-Mn(CO)ax bond occupied by a lone pair of electrons.
In the crystal lattice, discrete five-coordinated adducts around
Te exist with no additional secondary intermolecular interactions
from neighboring Cl and Te atoms (7.668(9) Å). This feature
is different from secondary interactions observed in the free Te4-
Cl16 in which significant intermolecular interactions are noted.15
Figure 1. ORTEP drawing and labeling scheme of the [Cl4Te-Mn-
(CO)5]- anion.
The slightly antiumbrella shape of the five ligands (4 Cl and 1
Mn(CO)5 fragment) to Te can be attributed to the steric influence
of the bulky Mn(CO)5 fragment (Mn-Te-Cl 91.21(23)-93.80-
(20)°). Actually, the four Cl- ligands and the Te atom are
almost constrained to a coplanar arrangement (Cl-Te-Cl 90.4-
(3)°, 88.43(25)°, 90.9(3)°, 89.9(3)°). The arrangement of the
four chlorides is symmetrica1 so that the Te-Mn-C(3)O(3)
vector lies on a 4-fold rotation axis. Two parallel groups, the
coplanar TeCl4 fragment and the coplanar Mn(CO)4 fragment,
are in a staggered conformation with torsion angle 44°.
The Te-Cl bond distances in [PPN][Cl4Te-Mn(CO)5], 2.549-
(7)-2.569(7) Å, compare well to those of [TeIVCl6]2- (Te-Cl
average distance 2.541(7) Å)1,16 and are distinctly longer than
the Te(IV)-Cl bonds, 2.31(1) Å in Te4Cl16,15 2.496 Å (average)
in [H9O4][TeCl4OH]‚H2O,1,5 2.538(4), 2.465(4), and 2.447(3)
Å in [(s)-2-Me2NCH(Me)C6H4]TeCl3,17 2.488(1)-2.550(1) Å
in Ph2P(NSiMe3)2TeCl3,18a and 2.525(4) and 2.499(3) Å in
[TeCl2(CH3OC6H4)(C8H11O2)].18b
The geometry around the Mn atom is a distorted octahedral
as expected. The Mn-Te bond of length 2.665(5) Å is slightly
shorter than the terminal Mn(I)-Te distances in cis-[Mn(CO)4-
(TePh)2]- (2.676(1) and 2.671(1) Å),10 in four-coordinate
[Mn(TePh)4]- (2.722-2.760 Å),19 in six-coordinate Mn(TeCH2-
Ph)(CO)3(PEt3)2 (2.705(1) Å),20 and in Mn[TeSi(SiMe3)3]2-
(dmpe) (2.679(2) Å).21a The average Mn-C distance, 1.88(4)
Å in [PPN][Cl4Te-Mn(CO)5], is comparable to the reported
Mn-C bond, 1.81 Å (average) in [Mn(CO)5]- 21b and 1.813(8)
Å in [Mn(CO)4(TePh)2]-.10
Formation of [Cl4Te-Mn(CO)5]- can be interpreted as coor-
dinative addition of the metalloanion [Mn(CO)5]- to TeCl4. It
may be attributed to the Lewis acid character of TeCl4 as well
as to the availability of a nonbonding electron pair of the
(12) The orange complex [PPN][(CO)3Mn(µ-Cl)3Mn(CO)3] crystallizes in
the monoclinic space group P21/n with a ) 9.692(3) Å, b ) 15.617-
(16) Hazell, A. C. Acta Chem. Scand. 1966, 20, 165.
(6) Å, c ) 29.637(9) Å, â ) 92.40(4)°, V ) 4482(3) Å3, dcalcd
1.526, Z ) 4, final R ) 0.080, and Rw ) 0.104.
)
(17) Singh, H. B.; Suclha, N.; Butcher, R. T. Inorg. Chem. 1992, 31, 1431.
(18) (a) Chivers, T.; Doxsee, D. D.; Gao, X.; Parvez, M. Inorg. Chem.
1994, 33, 5678. (b) Husebye, S.; Meyers, E. A.; Zingaro, R. A.;
Comasseto, J. V.; Penagnani, N. Acta Crystallogr. 1987, C43, 1147.
(19) Tremel, W.; Krebs, B.; Greiwe, K.; Simon, W.; Stephan, H.-O.; Henkel,
G. Z. Naturforsch. 1992, 47B, 1580.
(20) McGregor, K.; Deacon, G. B.; Dickson, R. S.; Fallon, G. D.; Rowe,
R. S.; West, B. J. Chem. Soc., Chem. Commun. 1990, 19, 1293.
(21) (a) Gindelberger, D. E.; Arnold, J. Inorg. Chem. 1993, 32, 5813. (b)
Rossi, A. R.; Hoffmann, R. Inorg. Chem. 1975, 14, 365.
(13) Cihonski, J. L.; Walker, M. L.; Levenson, R. A. J. Organomet. Chem.
1975, 102, 335.
(14) (a) Drew, D.; Darensbourg, D. J.; Darensbourg, M. Y. Inorg. Chem.
1975, 14, 1579. (b) Darensbourg, D. J.; Darensbourg, M. Y.; Drew,
D.; Conder, H. L. J. Organomet. Chem. 1974, 74, C33. (c) Liaw, W.-
F.; Chiou, S.-J.; Lee, W.-Z.; Lee, G.-H.; Peng, S.-M. J. Chin. Chem.
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(15) Buss, B.; Krebs, B. Angew. Chem., Int. Ed. Engl. 1970, 9, 463.

Notes
Inorganic Chemistry, Vol. 37, No. 5, 1998 1133
Table 1. Crystallographic Data of Complex
manganese atom in the [Mn(CO)5]-.22 The anionic [Cl4Te-
Mn(CO)5]- is of the 12-Te-5 class and illustrates the ability of
the tellurium to expand to incorporate 12 electrons in the valence
shell.23
In summary, the [Mn(CO)5]- anion may serve as a lone-
pair-electron donor, and the structural evidence suggests that
coordinative addition of [Mn(CO)5]- to TeCl4 leads to the
formation of a discrete chlorotellurate, [Cl4Te-Mn(CO)5]-.
[PPN][Cl4Te-Mn(CO)5]‚THF
chem formula
fw
cryst syst
space group
λ, Å (Cu KR)
a, Å
C45H38O6NP2Cl4MnTe
1075.09
monoclinic
P21/n
1.5406
9.180(3)
36.746(8)
13.869(4)
90.20(3)
4678.5(22)
4
1.526
103.927
25
b, Å
c, Å
â, deg
Experimental Section
V, Å3
Z
d
Manipulations, reactions, and transfers of samples were conducted
under nitrogen according to standard Schlenk techniques or in a
glovebox (Ar gas). Solvents were distilled under nitrogen from
appropriate drying agents (ethyl ether from CaH2; acetonitrile from
CaH2/P2O5; hexane and tetrahydrofuran (THF) from Na/benzophenone;
ethyl alcohol from CaH2) and stored in dried, N2-filled flasks over 4-Å
molecular sieves. A nitrogen purge was used on these solvents before
use, and transfers to reaction vessels were via stainless steel cannula
under N2 at a positive pressure. The reagents dimanganese decacar-
bonyl, tellurium(IV) chloride, and bis(triphenylphosphoranylidene)-
ammonium chloride (Aldrich) were used as received. Infrared spectra
were recorded on a spectrometer (Bio-Rad FTS-185, and FTS-7 FTIR)
with sealed solution cells (0.1 mm) and KBr windows. UV-vis spectra
were recorded on a GBC 918 spectrophotometer. Analyses of carbon,
hydrogen, and nitrogen were obtained with a CHN analyzer (Heraeus).
calcd, g cm-3
µ, cm-1
T, °C
Ra
0.097
0.108
2.42
b
Rw
GOFc
a R ) ∑|(Fo - Fc)|/∑Fo. b Rw ) [∑w(Fo - Fc)2/∑wFo ]1/2
.
c GOF )
2
[∑[w(Fo - Fc)2/(M - N)]1/2, where M ) number of reflections and N
) number of parameters.
Table 2. Selected Bond Distances (Å) and Angles (deg) for
[Cl4Te-Mn(CO)5]-
Mn-Te
2.665(5)
1.91(3)
1.86(3)
1.83(4)
1.92(3)
Te-Cl(1)
Te-Cl(2)
Te-Cl(3)
Te-Cl(4)
Mn-C(5)
2.552(7)
2.569(7)
2.555(8)
2.549(7)
1.86(3)
Mn-C(1)
Mn-C(2)
Mn-C(3)
Mn-C(4)
Preparation of [PPN][Cl4Te-Mn(CO)5]. [PPN][Mn(CO)5] (0.4
mmol, 0.294 g) and TeCl4 (0.4 mmol, 0.108 g) dissolved in 10 mL of
THF were stirred under nitrogen at -15 °C. A vigorous reaction
occurred immediately. IR spectra ν(CO): (THF) 2127 w, 2049 vs,
2009 m cm-1; (CH3CN) 2131 w, 2051 vs, 2031 m cm-1. Absorption
spectrum (MeOH) [λmax, nm (ꢀ, M-1 cm-1)]: 362 (4954). The light
green THF solution was layered with hexane; storage for 3 weeks at
-15 °C led to the formation of light green crystals of [PPN][Cl4Te-
Mn(CO)5]‚THF suitable for X-ray crystallography. The yield was
0.088 g (41%). The 125Te resonance could not be detected in the 125Te
NMR spectrum even at low temperature (-30 °C). Anal. Calcd for
C45H38O6TeCl4MnP2N: N, 1.30; C, 50.27; H, 3.56. Found: N, 1.42;
C, 49.95; H, 3.51. The light green crystals easily decomposed under
vacuum. The compound crystallized with THF solvent molecules,
which appeared to diffuse from the lattice within an hour of isolation.
After stirring of the [PPN][Cl4Te-Mn(CO)5] THF solution at ambient
Mn-Te-Cl(1)
Mn-Te-Cl(2)
Mn-Te-Cl(3)
Mn-Te-Cl(4)
Cl(l)-Te-Cl(2)
Te-Mn-C(1)
Te-Mn-C(2)
Te-Mn-C(3)
Te-Mn-C(4)
Te-Mn-C(5)
91.96(22)
91.82(23)
91.21(23)
93.80(20)
176.0(3)
88.4(10)
89.1(9)
178.0(11)
88.2(13)
88.2(9)
Cl(1)-Te-Cl(3)
Cl(1)-Te-Cl(4)
Cl(2)-Te-Cl(3)
Cl(2)-Te-Cl(4)
Cl(3)-Te-Cl(4)
C(1)-Mn-C(2)
C(1)-Mn-C(3)
C(1)-Mn-C(4)
C(1)-Mn-C(5)
90.4(3)
88.43(25)
90.9(3)
89.9(3)
174.9(3)
92.1(12)
90.2(15)
176.5(16)
90.5(12)
m cm-1) and [(CO)3Re(µ-Cl)3Re(CO)3]- (2016 s, 1914 vs cm-1) after
separation by THF-hexane.
Crystallography. Crystallographic data for the structure of the
complex [PPN][Cl4Te-Mn(CO)5] are collected in Table 1 and in the
Supporting Information. Bond distances and angles are collected in
Table 2. Crystals of [PPN] [Cl4Te-Mn(CO)5]‚THF used for the X-ray
diffraction structural determination were obtained from vapor diffussion
of (or layered with) hexane into concentrated THF solution at -15 °C
under a nitrogen atmosphere. The light green, very thin rectangular
plate crystal used for the study had approximate dimensions of ca. 0.05
× 0.50 × 0.60 mm. The crystal was mounted on a glass fiber and
quickly coated in epoxy resin at 25 °C. The thin-plate crystals [PPN]-
[Cl4Te-Mn(CO)5]‚THF decay during X-ray data collection (three
standard reflections were monitored every 3600 s, intensity decay 50%);
it is attributed to the THF solvent of crystallization. Several attempts
to grow crystals by adopting other organic solvents (CH3CN, MeOH,
CH2Cl2) were unsuccessful. The unit-cell parameters were obtained
from 25 reflections with 2θ between 40.20° and 83.64° for the product
[PPN][Cl4Te-Mn(CO)5]. Diffraction measurements were carried out
on a Nonius CAD 4 diffractometer with graphite-monochromated Cu
KR radiation, λ ) 1.5406 Å, employing the θ/2θ scan mode.24 A æ
scan absorption collection was made. Structural determinations were
made using the NRCC-SDP-VAX package of programs.25
temperature, two new bands (ν(CO) (THF) 2017 s, 1928 vs cm-1
)
appeared which were attributed to the formation of [PPN][(CO)3Mn-
(µ-Cl)3Mn(CO)3].12,13 The light green solution completely converted
into an orange solution with a precipitate of Te powder, and presumably
[PPN][Cl] overnight at ambient temperature. Solvent was removed
from the filtrate by vacuum, the orange powder was washed with
hexane, and recrystallization from THF-hexane gave orange crystals
of [PPN][(CO)3Mn(µ-Cl)3Mn(CO)3] suitable for X-ray crystallography,
0.131 g (71%). IR ν(CO): (THF) 2017 s, 1928 vs cm-1 12,13
.
Absorption spectrum (MeOH) [λmax, nm (ꢀ, M-1 cm-1)]: 379 (1211).
Anal. Calcd for C42H30O6Cl3Mn2P2N: N, 1.52; C, 54.66; H, 3.28.
Found: N, 1.80; C, 55.10; H, 3.65.
Reaction of TeCl4 and [Na-18-crown-6-ether][Re(CO)5]. Re2-
(CO)10 (0.2 mmol, 0.131 g), Na (0.4 mmol, 0.01 g), and 18-crown-6-
ether (0.4 mmol, 0.106 g) dissolved in 10 mL of THF were stirred
under nitrogen. Over a period of 2 h, the reaction mixture was added
to TeCl4 (0.4 mmol, 0.108 g) by cannula under positive N2 at -20 °C.
The reaction was monitored with FTIR. The IR spectra, ν(CO) (THF)
2007 m, 2046 s, 2139 w cm-1, indicated the formation of [Na-18-
crown-6-ether][Cl4Te-Re(CO)5]. The thermally unstable green solution
accompanied by black Te powder was stirred at room temperature; the
IR spectra revealed the formation Re(CO)5Cl (2130 vw, 2037 s, 1980
(24) North, A. C. T.; Philips, D. C.; Mathews, F. S. Acta Crystallogr. 1968,
A24, 351.
(25) (a) Gabe, E. J.; LePage, Y.; Chrarland, J. P.; Lee, F. L.; White, P. S.
J. Appl. Crystallogr. 1989, 22, 384. (b) Atomic scattering factors were
obtained from the following: International Tables for X-Ray Crystal-
lography; Kynoch Press: Birmingham, England, 1974; Vol. IV.
(22) Male, J. L.; Davis, H. B.; Pomeroy, R. K.; Tyler, O. R. J. Am. Chem.
Soc. 1994, 116, 9353.
(23) (a) Bogan, L. E., Jr.; Rauchfuss, T. B.; Rheingold, A. L. Inorg. Chem.
1985, 24, 3720. (b) Perkins, S. W.; Martin, J. C.; Arduengo, A. J.;
Lau, W.; Alegria, A.; Kochi, J. K. J. Am. Chem. Soc. 1980, 102, 7753.

1134 Inorganic Chemistry, Vol. 37, No. 5, 1998
Notes
Beq values, bond lengths and angles, and anisotropic temperature factors
for [PPN][Cl4Te-Mn(CO)5] (7 pages). An X-ray crystallographic file,
in CIF format is available on the Internet only. Ordering and access
information is given on any current masthead page.
Acknowledgment. We thank the National Science Council
(Taiwan) for support of this work. The authors thank Professor
Marcetta Y. Darensbourg and Professor Donald J. Darensbourg
for helpful discussion.
Supporting Information Available: Tables of crystal data and
experimental conditions for the X-ray studies, atomic coordinates and
IC9708677