Heteronuclear multiple bonding between heavier group 14 and 16 elements. A new class of germylated compounds, the germanethiocarbamyl and germaneselenocarbamyl chlorides L2(Cl)GeY (Y = S, Se)

Article abstract of DOI:10.1021/om0208974

The first monomeric germanethiocarbamyl halides containing a chelating β-diiminate ligand, L²(Cl)Ge=Y (L² = PhNC(Me)CHC(Me)NPh; Y = S (2), Y = Se (3)), have been prepared by the reaction of the corresponding heteroleptic halogermylene L²(Cl)Ge (1) with elemental sulfur or black selenium in refluxing toluene. Single-crystal X-ray structural analyses of 2 and 3 reveal that the germanium centers reside in highly distorted tetrahedral environments in these compounds; short Ge-Y distances (Ge-S = 2.07 A (2); Ge-Se = 2.21 A (3)) are indicative of an unsaturated character of these germanium-chalcogen bonds. Selective reactions between 2 or 3 and MeLi afforded the corresponding alkylated germanechalco-genones L²(Me)Ge=Y (Y = S (4), Se (5)).

Full text of DOI:10.1021/om0208974

1106
Organometallics 2003, 22, 1106-1109
Heter on u clea r Mu ltip le Bon d in g betw een Hea vier Gr ou p
14 a n d 16 Elem en ts. A New Cla ss of Ger m yla ted
Com p ou n d s, th e Ger m a n eth ioca r ba m yl a n d
Ger m a n eselen oca r ba m yl Ch lor id es L2(Cl)GeY (Y ) S, Se)
Isabelle Saur, Ghassoub Rima, Heinz Gornitzka, Karinne Miqueu, and
J acques Barrau*
Laboratoire He´te´rochimie Fondamentale et Applique´e, UMR 5069, Universite´ Paul Sabatier,
118, route de Narbonne, F-31062 Toulouse Cedex 04, France
Received October 29, 2002
The first monomeric germanethiocarbamyl halides containing a chelating â-diiminate
ligand, L2(Cl)GedY (L2 ) PhNC(Me)CHC(Me)NPh; Y ) S (2), Y ) Se (3)), have been prepared
by the reaction of the corresponding heteroleptic halogermylene L2(Cl)Ge (1) with elemental
sulfur or black selenium in refluxing toluene. Single-crystal X-ray structural analyses of 2
and 3 reveal that the germanium centers reside in highly distorted tetrahedral environments
in these compounds; short Ge-Y distances (Ge-S ) 2.07 Å (2); Ge-Se ) 2.21 Å (3)) are
indicative of an unsaturated character of these germanium-chalcogen bonds. Selective
reactions between 2 or 3 and MeLi afforded the corresponding alkylated germanechalco-
genones L2(Me)GedY (Y ) S (4), Se (5)).
In tr od u ction
turally characterized. These compounds are either
thermodynamically stabilized by coordination of Lewis
bases to the germanium3a,b,d,4a-c (tetra- or pentacoordi-
nate species) or kinetically stabilized using bulky pro-
tecting groups on the germanium3c,4d,e,5 (tricoordinate
species). The intrinsic character of the double bond in
the thermodynamically stabilized compounds depends
on the nature of the Lewis base. The species >MdY
have been obtained by different methods of synthesis.
Retrocycloaddition of 1,2,3,4-trithiagermolanes,6 reac-
tion of divalent germanium compounds with epi-
sulfides,3c,4b and desulfurization of 1,2,3,4,5-tetra-
thiagermolanes3c,4d,e are the three synthetic approches
to the kinetically stabilized Ar1Ar2GedY species. The
tetra- and pentacoordinate germanechalcogenones were
prepared by direct reaction of the corresponding ger-
mylene with the elemental chalcogen.3a,b,4a,c To our
knowledge, no halogenated and also no nitrogen-,
phosphorus-, oxygen-, or sulfur-substituted germanechal-
cogenones Σ(X)GedY (X ) Cl, Br, I; Σ ) NR2, PR2, OR,
SR) have been described to date, probably because only
a few monosubstituted halogermylenes have been char-
acterized until now, since such Σ(X)Ge species undergo
typical reactions in which Σ and X are redistributed if
the coordination site involved in the first step of this
exchange reaction is not blocked by another ligand. We
The doubly bonded compounds of the heavier group
14 elements >MdM<, >MdC<, >MdY (M ) Si, Ge,
Sn, Pb; Y ) O, S, Se, N-R) have been long considered
to be elusive intermediates, but experimental evidence
for the existence of multiply bonded group 14 metal
compounds has accumulated in the past few years so
that now the stabilization and the chemistry of such
species is well documented.1,2 Several species possessing
>MdM< and >MdC< moieties have been isolated
recently, but monomeric stable compounds containing
a double bond between heavier group 14 and group 16
elements still are much less numerous, particularly in
the case of germanium. Only four germanethiones,3,4e
seven germaneselones,3b,4 and four germanetellones3b,4a,5
have been isolated to date as stable species and struc-
(1) (a) Stage´, J . Adv. Organomet. Chem. 1982, 21, 241. (b) Cowley,
A. H. Polyhedron 1984, 3, 389. (c) Raabe, G.; Michl, J . Chem. Rev. 1985,
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Angew. Chem., Int. Ed. Engl. 1987, 26, 1201.
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10.1021/om0208974 CCC: $25.00 © 2003 American Chemical Society
Publication on Web 01/28/2003

A New Class of Germylated Compounds
Organometallics, Vol. 22, No. 5, 2003 1107
Sch em e 1
F igu r e 1. Solid-state structure of 2 (ellipsoids are drawn
at the 50% probability level). Selected bond lengths (Å) and
bond angles (deg): Ge-S ) 2.074(1), GeCl ) 2.184(1),
Ge-N ) 1.882(2), N-C(7) ) 1.345(3), C(7)-C(9) ) 1.386-
(3); N-Ge-N ) 98.14(12), N-Ge-Cl ) 103.03(6), N-Ge-S
) 118.17(6), Cl-Ge-S ) 113.77(4).
have recently reported the syntheses and different
aspects of the reactivity of stable divalent species of the
type Σ(X)GeII using as Σ monoanionic polydentate
ligands such as a phenoxy group bearing in the 2,4,6-
positions dimethylamino groups7 or a â-diiminate.8 In
our previous general report concerning the three-
coordinate divalent germanium compounds L2(X)Ge (L2
) PhNC(Me)CHC(Me)NPh; X ) Cl, I), we also have
briefly described the preparation of the corresponding
“germanechalcogenones”, L2(X)GedY, the first examples
of formal multiply bonded heavier group 14 elements
bearing a halide substituent.8 Herein we report the full
details of the syntheses and the structural characteriza-
tions, along with a preliminary assessment of the
reactivity, of these “halogenated germanechalcogenones”,
the first examples9 of organogermanethiocarbamyl and
organogermaneselenocarbamyl halides, compounds of
potential interest due to the presence of a halogen
substituent on the germanium atom.
F igu r e 2. Solid-state structure of 3 (ellipsoids are drawn
at the 50% probability level). Selected bond lengths (Å) and
bond angles (deg): Ge-Se ) 2.210(1), Ge-Cl ) 2.215(1),
Ge-N ) 1.880(3), N-C(7) ) 1.343(5), C(7)-C(9) ) 1.386-
(4); N-Ge-N ) 98.10(18), N-Ge-Cl ) 103.78(10), N-Ge-S
) 118.03(9), Cl-Ge-S ) 112.88(5).
199 °C (3)) and the presence of the molecular ion peaks
in their electronic impact (70 eV) mass spectra are
indicative of their thermal stability. Compound 3 is less
soluble than 1 and 2 in aromatic and even in polar
solvents (1 already has a very low solubility), preventing
an 77Se NMR study. Both compounds were fully char-
Resu lts a n d Discu ssion
Stoichiometric amounts of S8 or black Se were added
to saturated solutions of chlorogermylene L2GeCl (1) in
toluene (L2 ) PhNC(Me)CHC(Me)NPh) (Scheme 1). The
respective mixture was heated at reflux for 3 h and then
cooled to room temperature. Yellow diffraction-quality
single crystals of L2(Cl)GedS (2) and L2(Cl)GedSe (3)
grew slowly during this period (yields >80%). Com-
pound 1 does not react with tellurium under these
conditions.
1
acterized by H NMR, EI-MS, and elemental analysis.8
1H NMR spectra of 2 and 3 are quite similar to those of
the starting material L2Ge(Cl), the equivalence of the
two methyl and also of the two phenyl groups in the
NMR spectra of 2 and 3 indicating the presence of Cs-
symmetric species in solution.8 The solid-state struc-
tures of 2 and 3 were determined by single-crystal X-ray
diffraction. The molecular structures of compounds 2
and 3 are shown in Figures 1 and 2, respectively.
Crystallographic data and processing parameters are
given in Table 1.
The X-ray crystallographic analyses confirm that 2
and 3 exist as monomers in the solid state. The two
complexes have similar structural features; 2 and 3
show highly distorted tetrahedral geometries around the
germanium centers with the dihedral angles between
N(1)-Ge(1)-N(1) and Cl(1)-Ge(1)-S(1) being 90° in 2
and 3. The angles and bond lengths of these compounds
are consistent with mirror symmetry of the ligand
passing through the germanium, chlorine, carbon C(9),
and chalcogen atoms. Therefore, this ligand is sym-
Compounds 2 and 3 are stable under an inert atmo-
sphere. Their high melting points (172-173 °C (2); 198-
(7) (a) Barrau, J .; Rima, G.; El Amraoui, T. Organometallics 1998,
17, 607. (b) Barrau, J .; Rima, G.; El Amraoui, T. J . Organomet. Chem.
1998, 570, 163. (c) Barrau, J .; Rima, G.; El Amraoui, T. J . Organomet.
Chem. 1998, 561, 167.
(8) Akkari, A.; Byrne, J . J .; Saur, I.; Rima, G.; Gornitzka, H.; Barrau,
J . J . Organomet. Chem 2001, 622, 190.
(9) There had been no example of isolation of a germanechalcogeno-
carbamyl chloride until we preliminarily reported the syntheses of 2
and 38 and presented their structures (i) at the 6th International
Conference on Heteroatom Chemistry, Lodz, Poland, J une 22-27, 2001
(P 114) and (ii) at the Xth International Conference on the Coordination
and Organometallic Chemistry of Ge, Sn and Pb, Bordeaux, France,
J uly 8-12, 2001 (2P30). During the editing of this paper Roesky et al.
described the structures of two sulfur compounds [ArNC(Me)CHC(Me)-
NAr](X)GedS (X ) Cl, F), in which Ar is a sterically demanding
substituent (Ar ) 2,6-iPr2C6H5). (Ding, Y.; Ma, Q.; Uson, I.; Roesky,
H. W.; Noltemeyer, M.; Schmidt, H. G. J . Am. Chem. Soc. 2002, 124,
8542).

1108 Organometallics, Vol. 22, No. 5, 2003
Saur et al.
Sch em e 2
concerning H2GedY have predicted 2.04 Å for GedS and
2.17 Å for GedSe,5a whereas typical Ge-Y single-bond
distances are ∼2.26 Å (Y ) S) and ∼2.39 Å (Y ) Se),
respectively.3b In fact, the GedY bond lengths in 2 and
3 are slightly longer than those observed in the only
kinetically stabilized germanechalcogenones known to
date, Ar1Ar2GedY (Ar1 ) 2,4,6-tris[bis(trimethylsilyl)-
methyl]phenyl, Ar2 ) 2,4,6-triisopropylphenyl, Y ) S
(2.05 Å),3c Se (2.18 Å);4d Ar2 ) bis(trimethylsilyl)methyl,
Y ) Se (2.17 Å)4e). These distances can be compared to
those observed for the tetra- or pentacoordinate base-
F igu r e 3. Side view of 2 and 3.
Ta ble 1. Cr ysta l Da ta a n d Str u ctu r e Refin em en t
Deta ils for 2 a n d 3
2
3
empirical formula
fw
C
18H18Cl4GeN2S
C18H18Cl4GeN2Se
555.69
508.79
temp (K)
wavelength (Å]
cryst syst
space group
a (Å)
173(2)
173(2)
0.710 73
0.710 73
orthorhombic
Pnma
14.9919(9)
15.4408(9)
9.2238(6)
orthorhombic
Pnma
15.1574(13)
15.5540(3)
9.1975(8)
stabilized compounds LnGeY and L2GeY (Y ) S, Ln
)
η3-[(µ-ButN)2(SiMeNBut)2] (2.06 Å),3a η4-[Me8taa] (2.11
Å);3b Y ) Se, L ) η2-[(2-C5H4N)(Me3Si)2C] (2.25 Å),4a
η2-[(C6H11)NC(tBu)N(C6H11)] (2.20 Å),4b η2-[2-(C5H4N)-
(Me3Si)(Ph)C] (2.43 Å)4c). In fact, in these two com-
pounds the geometries around the Ge centers are
between distorted tetrahedrons and trigonal pyramids
since, as shown in Figure 3, the chalcogens deviate by
about 43° from the N(1)-Ge-N(1) planes and the Cl
centers by about 70°. Thus, these data suggest that the
germanium-chalcogen bonds in 2 and 3 can be consid-
ered as intermediate between those of the structures
containing formal group 16-group 14 element double
bonds (I) and those of the ylide forms presented (II),
considering that an amino group is a better nucleophile
than a chloride ion, in Scheme 2.
b (Å)
c (Å)
V (Å3)
2135.2(2)
4
2168.4(3)
4
1.702
3.590
1096
Z
calcd density (Mg/m3) 1.583
abs coeff (mm-1
)
2.038
F(000)
1024
cryst size (mm3)
θ range for data
collecn (deg)
0.2 × 0.3 × 0.4
0.4 × 0.5 × 0.6
2.57-24.71
2.57-26.41
range of hkl
-17 < h < 15
-17 < k < 18
-8 < l < 10
10373
1888 (Rint ) 0.0282) 2317 (Rint ) 0.0332)
semiempirical semiempirical
-18 < h < 18
-19 < k < 15
-11 < l < 11
13792
no. of rflns collected
no. of indep rflns
abs cor
max/min transmissn 1.000 000/0.773 640 1.000 000/0.599 268
The heteroleptic germanethiocarbamyl and germane-
selenocarbamyl chlorides are of interest, since the
presence of a halogen on the germanium atom offers
numerous possibilities for the synthesis of new and
unusual germylated species. The reactions of 2 and 3
with methyllithium are illustrative. We observed selec-
tive alkylation of germanium to give the germanechal-
cogenones L2(Me)GedY (Y ) S (4), Se (5)).
no. of indep data
no. of params
1888
128
1.043
0.0277
0.0673
0.869, -0.607
2317
134
1.063
0.0385
0.1021
1.631, -1.051
goodness of fit on F2
R1 (I > 2σ(I))
wR2 (all data)
largest diff peak,
hole (e Å-3
)
metrically bound to the germanium in 2 and 3. Contrary
to what is observed for L2Ge(Cl),10 the five ligand atoms
are coplanar, the planarity being confirmed by the fact
that the sums of the internal angles for the six-
membered L2Ge ring are exactly equal to 720° in 2 and
3 (Figure 3). The germanium atoms deviate from the
ligand plane (N(1A), C(7A), C(7), N(1)) by only 0.044 Å
(2) and 0.032 Å (3), respectively. A more marked
puckering is observed in 1, the corresponding distance
of 0.53 Å being more significant in this case.10
Due to the change of the germanium environment
(tricoordinate in 1, tetracoordinate in 2 and 3), the
Ge-N distances in 2 and 3 (1.88 Å) are shorter by 0.08
Å than those of the corresponding bond lengths of L2-
Ge(Cl). For the same reason the Ge-Cl distances in 2
(2.18 Å) and 3 (2.22 Å) are shorter than in 1 (2.34 Å).
The Ge-Y bond distances in 2 and 3 (Ge-S ) 2.07 Å
(2), Ge-Se ) 2.21 Å (3)) are more consistent with a
double than a single covalent bond, since calculations
Con clu sion
We have shown that â-diketiminato ligands are well-
suited for preparing germanechalcogenocarbamyl chlo-
rides, L2(Cl)GedY, underlining the influence of the
stabilizing ligand on the magnitude of the GedY
interaction. The â-diiminate ligand PhNC(Me)CHC(Me)-
NPh by its nucleophilicity and its structure appears to
permit to the germanium-chalcogen bond to obtain
double-bond character. It should be possible to modulate
this property by designing â-diketiminato ligands with
different electronic and steric properties. These mixed-
ligand species, L2(Cl)GedY, are of interest as possible
precursors of various unusual low-coordinate germa-
nium species.
Exp er im en ta l Section
All manipulations were carried out under an argon atmo-
sphere using standard Schlenk and high-vacuum-line tech-
niques. Solvents were distilled from conventional drying agents
(10) Chrostowska, A.; Lemierre, V.; Pigot, T.; Pfister-Guillouzo, G.;
Saur, I.; Miqueu, K.; Rima, G.; Barrau, J . Main Group Met. Chem.
2002, 25, 469.

A New Class of Germylated Compounds
Organometallics, Vol. 22, No. 5, 2003 1109
1
and degassed twice prior to use.11 The H and 13C NMR were
obtained as a green powder (0.23 g, 80%). Mp: 172-173 °C.1H
NMR: δ (ppm) 1.38 (s, 6H, Me), 4.66 (s, 1H, CH), 7.00-7.10
(m, 10H, Ph). EI-MS: m/z 390 (M•+). Anal. Calcd for C17H17N2-
ClSGe (Mr ) 389.454): C, 52.43; H, 4.39; N, 7.19. Found: C,
52.98; H, 4.68; N, 6.86.
L2(Cl)GedSe (3). Using the same experimental procedure
as for the synthesis of 2, the reaction of L2(Cl)Ge (0.25 g, 0.69
mmol) with elemental selenium (0.054 g, 0.69 mmol) gave 3
as a yellowish orange solid (0.25 g, 86%). Mp: 198-199 °C.
1H NMR: δ (ppm) 1.34 (s, 6H, Me), 4.67 (s, 1H, CH), 7.10-
7.18 (m, 10H, Ph). EI-MS: m/z 436 (M•+). Anal. Calcd for
recorded on Bruker AC-80 and AC-200 spectrometers. All
spectra were recorded in C6D6, and the chemical shifts δ are
relative to SiMe4. Mass spectra were recorded on a Nermag
R10-10H or a Hewlett-Packard 5989 instrument operating in
the electron impact mode at 70 eV, and samples were con-
tained in glass capillaries under argon. IR spectra were
obtained on a Perkin-Elmer 1600 FT-IR instrument. Irradia-
tions were carried out at 25 °C by using a low-pressure
mercury immersion lamp in a quartz tube. Melting points were
taken on a Leitz Biomed hot-plate microscope apparatus.
Elemental analyses (C, H, N) were performed at the Micro-
analysis Laboratory of the Ecole Nationale Supe´rieure de
Chimie de Toulouse.
C
17H17N2ClSeGe (Mr ) 436.344): C, 46.79; H, 3.92; N, 6.42.
Found: C, 46.12; H, 3.48; N, 6.81.
L2(Me)GedS (4). A solution of MeLi (1.6 M in ether, 0.4
mL, 0.64 mmol) was added to a stirred solution of L2Ge(Cl)S
(0.25 g, 0.64 mmol) in toluene (20 mL) at 80 °C. The reaction
mixture was stirred for 3 h. After filtration, the solvent was
removed under vacuum, and 3 was obtained as a yellow solid
X-r a y Cr ysta l Str u ctu r e Deter m in a tion of Com p ou n d s
2 a n d 3. Suitable yellow (2) and yellowish green (3) crystals
for X-ray diffraction experiments were obtained at low tem-
perature (-20 °C) by cooling concentrated chloroform solutions
of 2 and 3.
1
(0.1 g, 42%). Mp: 158-160 °C dec. H NMR: δ (ppm) 0.84 (s,
Crystal data for 2 and 3 are presented in Table 1. All data
were collected at low temperatures on a Bruker-AXS CCD
1000 diffractometer with Mo KR (λ ) 0.710 73 Å). The
structures were solved by direct methods by means of SHELXS-
9712 and refined with all data on F2 by means of SHELXL-
97.13 All non-hydrogen atoms were refined anisotropically. The
hydrogen atoms of the molecules were geometrically idealized
and refined using a riding model. Full details of the crystal-
lographic analysis of 2 and 3 are given in the Supporting
Information.
3H, Me), 2.01 (s, 6H, Me), 4.82 (s, 1H, CH), 7.30-7.43 (m, 10H,
Ph). 13C NMR: δ (ppm) 11.23 (Me), 20.60 (Me), 98.22 (CH),
125.07 (m aryl C), 126.21 (p aryl C), 128.38 (o-aryl C), 140.82
(C-N), 167.58 (Cipso). EI-MS: m/z 370 (M•+). Anal. Calcd for
C
18H20N2SGe (Mr ) 369.038): C, 58.58; H, 5.46; N, 7.59.
Found: C, 58.47; H, 5.31; N, 7.32.
L2(Me)GedSe (5). The same procedure as for 4 was used
1
for 5 (0.08 g, 30%). Mp: 140-142 °C dec. H NMR: δ (ppm)
1.01 (s, 3H, Me), 1.98 (s, 6H, Me), 4.80 (s, 1H, CH), 7.28-7.41
(m, 10H, Ph). 13C NMR: δ (ppm) 11.19 (Me), 20.40 (Me), 98.12
(CH), 124.81 (m aryl C), 126.12 (p aryl C), 127.75 (o aryl C),
140.32 (C-N), 167.21 (Cipso). EI-MS: m/z 416 (M•+). Anal. Calcd
for C18H20N2SeGe (Mr ) 415.928): C, 51.98; H, 4.85; N, 6.74.
Found: C, 51.63; H, 4.78; N, 6.82.
L2(Cl)GedS (2). A solution of L2(Cl)Ge (0.29 g, 0.81 mmol)
in toluene (10 mL) was added to a suspension of elemental
sulfur (0.026 g, 0.81 mmol) in toluene (5 mL). The reaction
mixture was heated at reflux for 3 h, during which time the
reaction mixture became red. After removal of all volatiles the
residue was washed with pentane and the product 2 was
Su p p or tin g In for m a tion Ava ila ble: Tables giving X-ray
crystallographic data and figures giving additional ORTEP
views of compounds 2 and 3. This material is available free of
charge via the Internet at http://pubs.acs.org.
(11) Perrin, D. D.; Armarego, W. L. F. F.; Perrin, D. R. Purification
of Laboratory Chemicals; Pergamon Press: New York, 1985.
(12) Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, 467.
(13) Sheldrick, G. M. SHELXL-97, Program for Crystal Structure
Refinement; Universita¨t Go¨ttingen, Go¨ttingen, Germany, 1997.
OM0208974