Low coordinate germanium and tin compounds (ArO)2M=E and (ArO)2M=M′Ln M=Ge, Sn; E=S, Se, -NSiMe3 M′=Cr, W, Fe, Pt [Ar=2,4,6-tris((dimethylamino)methyl)phenyl-]

Article abstract of DOI:10.1016/S0022-328X(98)00743-8

The reactions of the divalent species (ArO)₂M (Ar=2,4,6-[(CH₃)₂NCH₂]₃C ₆H₂; M=Ge, Sn) with either Me₃SiN₃, elemental S₈, Se or transition metal complexes M′(CO)_n+1 (M′=Fe, n=4; M′=Cr, W; n=5) (Ph₃P)₂Pt·C₂H₄ have resulted in the isolation of either the new stable formal metallanimines (ArO)₂M=N-SiMe₃, germanethione, -selone (ArO)₂Ge=E (E=S, Se) (the expected formations of the stannanethione and -selone were not observed), or the (ArO)₂M=M′(CO)_n, (ArO)₂M=Pt(PPh₃)₂ complexes, respectively. The direct oxidation of the (ArO)₂M species with various oxidizing agents led to the formation of the corresponding metalloxanes [(ArO)₂M-O-]₂. All of the chalcogenido- and transition metal-metal 14 complexes have been physicochemically and chemically characterized. The reactions of the (ArO)₂Ge=E (E=S, Se) compounds with 3,5-di-tert-butyl-1,2-benzoquinone produced, by extrusion of sulfur or selenium, the dioxametalloles corresponding to the formal addition of the divalent species (ArO)₂M to the benzoquinone. A substitution reaction of chalcogen (S/Se) has been observed permitting to go from germaneselone to germanethione.

Full text of DOI:10.1016/S0022-328X(98)00743-8

Journal of Organometallic Chemistry 570 (1998) 163–174
Low coordinate germanium and tin compounds (ArO)2MꢀE and
(ArO)2MꢀM%Ln M=Ge, Sn; E=S, Se, –NSiMe3 M%=Cr, W, Fe, Pt
[Ar=2,4,6-tris((dimethylamino)methyl)phenyl-]
Jacques Barrau *, Ghassoub Rima, Tajani El Amraoui
He´te´rochimie Fondamentale et Applique´e, UPRES-A 5069 du CNRS, Uni6ersite´ Paul-Sabatier, 118 route de Narbonne,
31062 Toulouse Cedex, France
Received 2 February 1998
Abstract
The reactions of the divalent species (ArO)2M (Ar=2,4,6-[(CH3)2NCH2]3C6H2; M=Ge, Sn) with either Me3SiN3, elemental S8,
Se or transition metal complexes M%(CO)n+1 (M%=Fe, n=4; M%=Cr, W; n=5) (Ph3P)2Pt·C2H4 have resulted in the isolation
of either the new stable formal metallanimines (ArO)2MꢀN–SiMe3, germanethione, -selone (ArO)2GeꢀE (E=S, Se) (the expected
formations of the stannanethione and -selone were not observed), or the (ArO)2MꢀM%(CO)n, (ArO)2MꢀPt(PPh3)2 complexes,
respectively. The direct oxidation of the (ArO)2M species with various oxidizing agents led to the formation of the corresponding
metalloxanes [(ArO)2M–O–]2. All of the chalcogenido- and transition metal–metal 14 complexes have been physicochemically
and chemically characterized. The reactions of the (ArO)2GeꢀE (E=S, Se) compounds with 3,5-di-tert-butyl-1,2-benzoquinone
produced, by extrusion of sulfur or selenium, the dioxametalloles corresponding to the formal addition of the divalent species
(ArO)2M to the benzoquinone. A substitution reaction of chalcogen (S/Se) has been observed permitting to go from ger-
maneselone to germanethione. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Metallanimine; Germanethione; Germaneselone; Transition metal complexes of M14 divalent species
1. Introduction
stabilized; the chemistry of these species is mainly
chemistry [15–17,22–29] of transient species and, in
fact, we only know 14 stable species of the type metal-
lanones, metallanethiones, -selones or -tellones [25,30–
37] so far.
During the past few years several transition metal
complexes have been used as catalysts in reactions of
formation, or cleavage, of M–M bonds for the synthe-
sis of precursors of new materials. Mechanisms involv-
ing intermediate [metallic divalent species–transition
metal] complexes have been postulated to explain the
role of the catalysts [38–42], thus renewing the re-
searchers interest for metallic analogs of carbenic com-
plexes of transition metals [43–64]; for reviews see
([47]a, [49]a, [49]b, [50,55], [61]a).
The poor tendency of main group elements to give
multiple bonds is perfectly illustrated by the behavior of
the Group 14 elements [1–5]. Compounds with SiꢀSi
bond, for example, are rare [6–8] and the first stable
disilene was obtained only in 1981 [6]. However, nu-
merous studies of metal 14 compounds involved in
multiple bonds have appeared in the past 10 years and
various stable derivatives of the types ꢁMꢀCꢂ,
ꢁMꢀMꢂ and ꢁMꢀE have been described (silicon
[9–13]; germanium [13–17]; Group 14 elements
[7,13,14,18]; Group 14 and 15 elements [19–21]). More
uncommon are the structures ꢁMꢀE which could be
The species ꢁMꢀE and the complexes ꢁMꢀM%Ln
can be obtained via different methods of synthesis.
* Corresponding author. Tel.: +33 5 61558224; fax: +33 5
618234; e-mail: barrau@ramses.ups-tlse.fr
0022-328X/98/$ - see front matter © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00743-8

164
J. Barrau et al. / Journal of Organometallic Chemistry 570 (1998) 163–174
However, the direct reaction of divalent species ꢁM
with E or a transition metal appears to be the better
method in both cases, provided the divalent species
are stable or metastable under the experimental condi-
tions.
In this context, we consider the stable divalent
(ArO)2M [M=Ge 1, M=Sn 2] species whose synthe-
ses and some aspects of their reactivity have been
described [65] as precursors of type ꢁMꢀE and
ꢁMꢀM%Ln species. Some preliminary aspects of this
work have been communicated earlier ([65]a)(ArO)2
MꢀE; (ArO)2 MꢀM%Ln M=Ge, Sn; Ar=2,4,6,-
[(CH3)2NCH2]3C6H2 E=S, Se, -NSiMe3; M%=Fe, Cr,
W; Ln=(CO)n(PPh3)2.
Scheme 2.
2. Results and discussion
2.1. Metallanimines (ArO)2MꢀN–SiMe3
tramolecular coordination between the dimethylamino
side chains to the metal atom, or a non static nitro-
gen…metal 14 interaction, to account for the mag-
netic equivalence of the o-NMe2 groups. We believe
that the same N…M…N dynamic coordination phe-
nomenon observed for the parent divalent species
(ArO)2M, [65] must be responsible for the equivalence
of the o-NMe2 groups. Thus these metallanimines
probably have a molecular structure included between
the limiting forms portrayed in Scheme 3, nevertheless
we were not able to define the true nature of the
interaction between the NMe2 groups and the Group
14 atom since crystals suitable for X-ray structural
analysis could not be obtained.
The germa- and stannanimines 3, 4 have been ob-
tained in excellent yields by the reaction of the diva-
lent species (ArO)2M with trimethylsilylazide
Me3SiN3. The nucleophilic attack of the azide on the
divalent species probably leads to a dipolar intermedi-
ate which decomposes into nitrogen and germanimine
(Scheme 1).
In these reactions, we could not detect any traces of
tetraazene resulting from the 1-3 addition of the
metallanimines to the trimethylsilylazide as has al-
ready been observed [16].
Cryoscopic mass determination showed that 3 and
4 are monomeric in benzene solution; they have been
physicochemically characterized by 1H-, 13C-, 119Sn-
NMR, IR, and mass spectroscopy and chemically by
reaction with protic reagents (Scheme 2).
2.2. Metallanones, metallanethiones, -selones and
-tellones
For complexes 3 and 4, the 1H-NMR spectra at
ambient temperature exhibit one broad singlet as sig-
nal for the four o-NMe2 groups along with a singlet
for the two corresponding p-NMe2 groups. This sug-
gests a structure for these metallanimines without in-
2.2.1. Metallanones
The direct oxidation of the divalent species
(ArO)2M by pure oxygen, DMSO, or N-pyridine ox-
ide leads to the corresponding metalloxanes 9 and 10
with various yields. Pure oxygen reacts at room tem-
perature (r.t.) in a quasi-quantitative way with 1 and
2 leading to the cyclic oxides 9 and 10, respectively,
probably via transient metallanones [(ArO)2MꢀO].
With DMSO and N-pyridine oxide, the reaction oc-
curs only at high temperature leading to 9 and 10,
with low yield (Scheme 4).
It is noteworthy that the dihalogenated germylenes
GeX2 react exothermally with the same oxidation
reagents [16]; the low reactivity of 1 and 2 towards
DMSO and PhNO points to a loss of electrophilic
character of the metal in the divalent species
(ArO)2M, this metal probably being engaged in in-
tramolecular coordinations N…M…N with the o-
dimethylamino side chains of the phenyl groups.
Scheme 1.

J. Barrau et al. / Journal of Organometallic Chemistry 570 (1998) 163–174
165
Scheme 3.
2.2.2. Metallanethiones
Complex 11 being inert towards isolated carbonyl
groups like Ph2CꢀO and (CH3)2CꢀO, addition probably
proceeds, like in the germylene case, through a one-
electron transfer mechanism since a transitory o-
semiquinonic radical structure has been characterized
by ESR spectroscopy in this reaction (toluene, −40°C,
g=2.0016, aH=2.9 G). The germanium–sulfur bond
of 11, like various Ge–Y (Y=H, Cl, N) bonds [66–69]
species, could act as electron-donor to the quinone and
the mechanism summarized by Scheme 6 is therefore
postulated to account for the formation of 14.
Here again, the presence of (dimethylamino)methyl
groups on the benzenic structure, giving to 11 a rather
zwitterionic character, seem to be responsible for the
loss of the characteristic aspects of the chemistry of
(free transient or stabilized only by steric effect) ger-
manethiones. Thus the stability and the reactivity which
have been observed could be explained by a molecular
structure of germanethione 11 included between the
two mesomeric limiting forms A and B shown in
Scheme 7. Such structures have been postulated for the
silicon and tin series ([48]c, [54]b, [59]b). Only X-ray
structural analysis of 11 could permit the identification
of the correct nature of the germanium–sulfur bond in
this compound, but we were unable to obtain crystals
suitable for X-ray study.
2.2.2.1. Case of germanium. Like oxygen, molecular
sulfur reacts with germylene (ArO)2Ge; the reaction is
carried out in benzene at 80°C (Scheme 5). But in this
case the species formed, 11, is monomeric in benzene
solution (cryoscopic mass determination), thermally
stable and can be perfectly physicochemically and
chemically characterized.
Complex 11 exhibits a moderate reactivity; the protic
reagents such as water and methanol react in a nearly
quantitative way with 11 leading to thiols 12 and 13,
respectively, but we could not observe any insertion
reactions in various small strained heterocycles or any
[2+4] or [2+2] cycloaddition with electron-poor or
-rich dienes.
With the 3,5-di-tert-butyl-1,2-benzoquinone we ob-
served an immediate reaction leading, (besides sulfur)
to the single product dioxagermole 14 which is the
formal adduct of the germylene (ArO)2Ge and the
quinone (Scheme 5).
Scheme 4.
Scheme 5.

166
J. Barrau et al. / Journal of Organometallic Chemistry 570 (1998) 163–174
Scheme 6.
2.2.2.2. Case of tin. For the same experimental condi-
tions as in the previous case, the reaction between the
divalent tin species (ArO)2Sn and sulfur S8 does not
lead to the formation of the corresponding stan-
nanethione since in the reaction of 2 with sulfur the
starting materials were recovered with any transforma-
tion (Eq. 1).
maneselone (ArO)2GeꢀSe (Eq. 2). Like its sulfur ho-
molog this species is stable, monomeric in benzene
solution (cryoscopic mass determination), and was
characterized by NMR (1H-, 13C-) and mass
spectroscopy.
C H
(ArO)2Ge+Se “6(ArO)2Ge=Se
(2)
6
80°C
(15)
The analysis of mass spectroscopy obtained under
electronic impact (70 eV) notably reveals the presence
of two series of lines corresponding to the molecular
[M]+ ion and [M–Se]+ ion. Since the fragmentation
’
This, obviously, reveals the instability of the
(ArO)2SnꢀS species since the addition of sulfur to tin is
not kinetically forbidden.
process of a molecule under electronic impact is corre-
lated to its behavior under thermal effect, the presence
of the signal [M–Se]+ in the spectrogram of 15 as
largely the most intense peak suggests the thermal
instability of the germanium–selenium bond in this
germaneselone (Eq. 3).
2.2.3. Metallaneselones
2.2.3.1. Case of germanium. The complex (ArO)2Ge and
black selenium lead, at 80°C in benzene, to the ger-
D
(ArO)2GeꢀSe“(ArO)2Ge+Se
(3)
The chemical reactivity of this germaneselone is quite
similar to the corresponding germanethione; we ob-
served the same types of reactions with water, methanol
and quinones (Scheme 8).
Thus a structure with a zwitterionic tendency could
be attributed to the germaneselone as in the ger-
manethione case (Scheme 9).
A substitution reaction of chalcogen could be ob-
served from this germaneselone (Eq. 4). In fact, when
we investigated the reaction of S8 with germaneselone
at 80°C in pure benzene, an exchange reaction between
selenium–sulfur occurs, allowing the production from
germaneselone of the germanethione probably via the
divalent species (ArO)2Ge.
Scheme 7.

J. Barrau et al. / Journal of Organometallic Chemistry 570 (1998) 163–174
167
This reaction is consistent with the respective mass
(ArO)2M divalent species are excellent |-donors and
thus have been used as ligands in transition metal
complexes. With (ArO)2M species, various complexa-
tion reactions could be achieved with complexes of
spectra of the two (ArO)2GeꢀX species. The relation
+
between [M]+ /[M–X]
is more important for
’
(ArO)2GeꢀS than for (ArO)2GeꢀSe, which indicates
that the energy of the GeꢀSe bond is lower than the
GeꢀS bond.
transition
metals
such
as
Fe(CO)4 ·THF,
W(CO)5 ·THF, Cr(CO)5 ·THF and C2H4 ·Pt(PPh3)2
(Scheme 10). In all cases, after liberation of THF or
ethylene, the reaction leads to the expected complexes
18–24.
Complexes 18–25 are colored solids, soluble in aro-
matic solvents, insoluble in pentane, having a great
sensitivity to oxygen and moisture. Cryoscopic mass
determination showed that 18–23 are monomeric in
C6H6; 18–25 have been characterized by NMR (1H-,
13C-, 31P-, 119Sn-), mass and IR spectroscopy (Table 1)
but unfortunately it was also impossible in these cases
to obtain, from various solvents at −20°C, crystals
suitable for crystallography.
IR spectra for compounds 18 and 19 show the ap-
pearance of three carbonyl bands, with the usual inten-
sity pattern for the (tBuS)2SiFe(CO)4 ·HMPA ([49]c)
species, which is characteristic of a C3v local symmetry
at iron with an axial coordination of the divalent
species on the iron (Scheme 11).
For complexes 20–23, the existence of three bands in
the IR spectra and of two 13C-NMR peaks for the CO
groups are compatible with molecular models with a
C4v symmetry (Scheme 12).
2.2.3.2. Case of tin. Similar to sulfur, in the same
experimental conditions, selenium is unreactive towards
the divalent species (ArO)2Sn, which again probably
reveals the thermal instability of the species
(ArO)2SnꢀSe (Eq. 5).
2.3. Complexes (ArO)2MꢀM%Ln [M=Ge, Sn;
M%Ln=Fe(CO)4, W(CO)5, Cr(CO)5, Pt(PPh3)2]
Superior analogs of carbenes, the divalent derivatives
(ArO)2M can be used as ligands in transition metal
chemistry. The stability of carbene-transition metal
complex is often explained by a |, y synergetic effect,
the |-donor effect on the metal of the free pair of
carbone being compensated by the p-donor effect of the
occupied orbital of the metal on the p vacant orbital of
the carbon atom. This concept is not easily applicable
to ꢁM–M%Ln complexes, since the ꢁM divalent spe-
cies are low p-y acceptors (no coordination of a diva-
lent species carrying a Lewis base to a transition metal
resulted in loss of the base complexing the divalent
species).
The mass spectra of complexes 18–23 exhibit peaks
corresponding to molecular ions M+ (weak intensity)
’
and to the characteristic fragmentations of such struc-
tures (loss of carbonyl groups and of substituents on
the Ge and Sn atoms, in particular).
Nevertheless, similar to all divalent organic deriva-
tives of the heavier main Group 14 elements, the
In all cases, we notice the equivalence of the four
o-NMe2 groups in H-NMR under an ambient temper-
1
Scheme 8.

168
J. Barrau et al. / Journal of Organometallic Chemistry 570 (1998) 163–174
solvents were dried by distillation from Na/K alloy and
1
deoxygenated by standard methods. H-NMR spectra
were recorded on a Bruker AC 80 spectrometer operat-
ing at 80 MHz (chemical shifts are given in ppm (l)
relative to Me4Si), 13C- spectra on a AC-200 MHz
spectrometer; the multiplicity of the 13C-NMR signals
was determined by the APT technique and quoted as
(+) for CH3 or CH, (−) for CH2 and (Cquat) for
quaternary carbon atoms. 31P-NMR spectra were mea-
sured on a Bruker AC-200 MHz (spectrometer fre-
quency 81.015 MHz). The 31P chemical shifts are
externally referenced to 85% H3PO4. 119Sn{1H}-NMR
spectra were recorded on a Bruker AC-200 or 400 MHz
(spectrometer frequency 74.63 or 149.21 MHz, chemical
shifts are reported in ppm (l) relative to external
Me4Sn as reference). Mass spectra were recorded on a
Nermag R10-10H or a Hewlett Packard 5989 instru-
ment operating, in the electron impact mode at 70 and
30 eV and samples were contained in glass capillaries
under argon, or in the chemical ionization mode (CH4).
IR spectra were obtained on a Perkin-Elmer 1600 FT-
IR. Irradiations were carried out at 25°C by using a
low-pressure mercury immersion lamp in a quartz tube.
Reactions under ultrasonic wave were carried out at 47
MHz using a Bransonic B 2200E apparatus. Melting
points were taken on a hot-plate microscope apparatus
Leitz Biomed. Elemental analyses (C, H, N) were per-
formed at the Microanalysis Laboratory of the Ecole
Nationale Supe´rieure de Chimie de Toulouse.
Scheme 9.
ature. Thus, the observation of a single sharp methyl
resonance for the o-NMe2 groups is characteristic of a
‘flip-flop’ N…M…N dynamic coodination mode, simi-
lar to the one observed for the precursors (ArO)2M
[65].
The monomeric structure of 24 has been confirmed
by 31P-NMR, since no coupling J(Pt–P) characteristic of
3
a dimeric structure has been observed. Thus 24 is likely
to have a planar triangular structure of three groups
around the platinum metal (Scheme 13).
All these complexes, with strongly polar metal 14-
transition metal bonds, appear as precursors with high
potential in organometallic synthesis. They can either
behave like precursors of divalent species or can lead to
the expected reactions for compounds with Group 14
metal-transition metal bonds, particularly towards oxy-
gen, CO2, CS2 and unsaturated systems for instance;
these reactions and silicon grafting reactions are now
under investigation.
3.2. Germanimine (ArO)2GeꢀN–SiMe3 (3)
A solution of trimethylsilylazide (0.03 g, 0.26 mmol)
in 10 ml of benzene was added dropwise to a solution
of (ArO)2Ge (0.16 g, 0.26 mmol) in 15 ml of benzene.
Nitrogen evolved immediately and the solution turned
to yellow. The mixture was stirred at r.t. for 20 h and
dried in vacuo giving a yellow residue which was ex-
tracted with 20 ml of pentane. After cooling to −20°C
complex 3 was filtered off as yellow crystals and dried
in vacuo (0.12 g, 70%).
3. Experimental section
3.1. General procedures
All reactions and manipulations were carried out
under an argon or nitrogen atmosphere with the use of
standard Schlenk and high-vacuum line techniques. All
1
Complex 3: m.p. 144–145°C. H-NMR (C6D6): 0.24
Scheme 10.

J. Barrau et al. / Journal of Organometallic Chemistry 570 (1998) 163–174
169
Table 1
Spectroscopic data for compounds 18–23
NMR (C6D6; l ppm)
Ge
(18)
(20)
(22)
Sn
(19)
(21)
(23)
1H
p-NMe2
o-NMe2
p-CH2N
o-CH2N
C6H2
2.07
2.19
3.36
3.54
7.15
2.07
2.19
3.36
3.53
7.23
2.06
2.19
3.34
3.51
7.22
2.18
2.24
3.26
3.49
7.24
2.04
2.18
3.35
3.51
7.22
2.05
2.19
3.34
3.50
7.21
13C
p-NMe2
o-NMe2
p-CH2N
o-CH2N
44.96
45.49
60.33
44.79
45.39
60.28
44.71
45.36
60.19
45.09
45.72
60.23
44.72
45.32
60.28
44.87
45.38
60.29
64.46
64.02
63.95
64.06
63.97
64.10
C6H2
127.07
128.61
129.37
157.42
211.30
214.62
127.07
128.60
129.37
157.04
197.15
200.05
126.92
128.33
129.05
157.18
218.40
221.14
127.65
128.66
130.39
157.91
216.93
218.76
127.60
128.29
130.57
157.65
213.77
215.53
127.48
128.08
130.15
157.96
219.39
223.56
CO
19Sn
−225.9
−391.2
−213.29
IR (C6H6, wCO cm−1
)
1984
1968
1887
1981
1948
1867
2092
1954
1914
2001
1946
1893
1974
1933
1859
2087
1935
1889
(s, 9H, SiMe), 2.06 (s, 24H, NMe), 2.13 (s, 12H, NMe),
3.29 (s, 4H, CH2), 3.38 (s, 8H, CH2), 7.27 (s, 4H, C6H2).
13C-NMR (C6D6): 2.83 (+), 44.92 (+), 45.47 (+),
60.81 (−), 64.61 (−), 125.71 (Cquat), 127.30 (+), 131.68
(Cquat), 160.8 (Cquat). MS: m/z=644 [M–3Me]+. IR
(C6H6, cm−1): wGeꢀN=1090. Anal. Found: C, 57.42; H,
8.74; N, 14.08. C33H61N7O2SiGe. Calc.: C, 57.59; H, 8.87;
N, 14.25.
(s, 4H, CH2), 3.41 (s, 8H, CH2), 7.26 (s, 4H, C6H2). MS:
m/z=662 [M–3Me]+. IR (C6H6, cm−1): wOH, wNH
3330–3438. Anal. Found: C, 56.08; H, 8.86; N, 13.76.
C33H63N7OSiGe. Calc.: C, 56.12; H, 8.92; N, 13.88.
=
3.4. Reaction of 3 with methanol
To a solution of 3 (0.1 g, 0.14 mmol) in 5 ml of benzene
was added an excess of MeOH (0.009 g, 0.28 mmol)).
Progressively, the color of the mixture changed. The
solvent was removed in vacuo. Crystallization from
pentane (ca. 10 ml) afforded 7 (0.08 g, 87%).
3.3. Reaction of 3 with H2O
H2O (0.002 g, 0.14 mmol) was added to a stirred
solution of 3 (0.1 g, 0.14 mmol) in 20 ml of benzene. The
volatile material was removed in vacuo affording a white
solid. Crystallization from pentane (ca. 20 ml) yielded 5
as a white crystals (0.09 g, 90%).
1
Complex 7: m.p. 127–128°C. H-NMR (C6D6): 0.28
(s, 9H, SiMe), 2.14 (s, 12H, NMe), 2.19 (s, 24H, NMe),
3.34 (s, 4H, CH2), 3.42 (s, 8H, CH2), 3.69 (s, 3H, OMe),
7.26 (s, 4H, C6H2). 13C-NMR (C6D6): 2.79 (+), 44.67
(+), 45.28 (+), 53.90 (+), 59.90 (−), 64.61 (−),
125.65 (Cquat), 127.12 (+), 131.48 (Cquat), 159.70
Complex 5: m.p. 134–135°C. 1H-NMR (C6D6): 0.3 (s,
9H, SiMe), 2.12 (s, 12H, NMe), 2.18 (s, 24H, NMe), 3.33
Scheme 11.
Scheme 12.

170
J. Barrau et al. / Journal of Organometallic Chemistry 570 (1998) 163–174
mmol). The volatiles were removed in vacuo. Crystalliza-
tion from pentane (ca.10 ml) and filtration gave 8 (0.08
g, 85%).
Complex 8: m.p. 137–138°C. 119Sn{1H} (C6D6): −
182.6. 1H-NMR (C6D6): 0.31 (s, 9H, SiMe), 2.14 (s, 24H,
NMe), 2.20 (s, 12H, NMe), 3.39 (s, 4H, CH2), 3.41 (s,
8H, CH2), 3.55 (s, 3H, OMe), 7.24 (s, 4H, C6H2).
13C-NMR (C6D6): 2.91 (+), 45.65 (+), 46.98 (+),
51.05 (+), 60.26 (−), 65.85 (−), 127.55 (Cquat), 129.82
(+), 131.48 (Cquat), 160.20 (Cquat). MS: m/z=767 [M]+
.
’
IR (C6H6, cm−1): wNH=3332. Anal. Found: C, 53.12; H,
8.36; N, 12.65. C34H65N7O3SiSn. Calc.: C, 53.28; H, 8.48;
N, 12.79.
Scheme 13.
(Cquat). MS: m/z=721 [M]+ . IR (C6H6, cm−1): wNH
=
’
3.8. Oxidation reaction of 1 and 2
3325. Anal. Found: C, 56.49; H, 8.92; N, 13.43.
C34H65N7O3SiGe. Calc.: C, 56.69; H, 9.03; N, 13.62.
3.8.1. Reaction with oxygen
Dry oxygen was bubbled through a solution of 1 (0.3
g, 0.5 mmol), or 2 (0.323 g, 0.5 mmol), in 15 ml of benzene
for 2 h. The solvent was evaporated in vacuo affording
9, or 10, which were purified by crystallization from
pentane (ca. 5 ml). Complex 9 (0.29 g, 94%); 10 (0.31 g,
94%).
3.5. Stannanimine (ArO)2SnꢀN–SiMe3 (4)
A solution of trimethylsilylazide (0.05 g, 0.46 mmol)
in 10 ml of benzene was added dropwise to a solution
of (ArO)2Sn (0.2 g, 0.46 mmol) in 20 ml of benzene.
Nitrogen evolved immediately and the solution turned to
yellow. The mixture was stirred for a further 20 h at r.t.
The solvent was removed in vacuo, affording a yellow–
orange powder which was dissolved in pentane (ca. 25
ml). After cooling to −20°C 4 was filtered off and dried
in vacuo (0.21 g, 65%).
1
Complex 9: m.p. 214–215°C. H-NMR (C6D6): 2.06
(s, 24H, NMe), 2.18 (s, 12H, NMe), 3.33 (s, 8H, CH2),
3.52 (s, 4H, CH2), 7.21 (s, 4H, C6H2). 13C-NMR (C6D6):
45.22 (+), 45.59 (+), 60.16 (−), 64.01 (−), 127.95
(Cquat), 129.17 (+), 131.87 (Cquat), 158.52 (Cquat). MS:
m/z=1190 [M–NMe2]+. IR (C6H6, cm−1): wGe–O
=
Complex 4: m.p. 150–151°C. 119Sn{1H}-NMR (C6D6):
842. Anal. Found: C, 58.22; H, 8.36; N, 13.49.
C60H104N12O6Ge2. Calc.: C, 58.38; H, 8.43; N, 13.62.
Complex 10: m.p. 228–229°C. 119Sn{1H}-NMR
1
−138.3. H-NMR (C6D6): 0.25 (s, 9H, SiMe), 2.08 (s,
24H, NMe), 2.19 (s, 12H, NMe), 3.36 (s, 4H, CH2), 3.52
(s, 8H, CH2), 7.19 (s, 4H, C6H2). 13C-NMR (C6D6): 3.13
(+), 46.59 (+), 47.29 (+), 61.46 (−), 66.11 (−),
127.55 (Cquat), 129.96 (+), 139.55 (Cquat), 160. 41 (Cquat).
1
(C6D6): −148.7. H-NMR (C6D6): 2.07 (s, 24H, NMe),
2.19 (s, 12H, NMe), 2.35 (s, 8H, CH2), 3.53 (s, 4H, CH2),
7.22 (s, 4H, C6H2). 13C-NMR (C6D6): 45.42 (+), 45.67
(+), 60.21 (−), 64.06 (−), 128.09 (Cquat), 129.29 (+),
132.57 (Cquat), 157.91 (Cquat). MS: m/z=1282 [M–
NMe2]+. IR (C6H6, cm−1): wSn–O=870. Anal. Found:
C, 54.16; H, 7.68; N, 12.49. C60H104N12O6Sn2. Calc.: C,
54.32; H, 7.84; N, 12.67.
MS: m/z=735 [M]+ . IR (C6H6, cm−1): wSnꢀN=1100.
’
Anal. Found: C, 53.79; H, 8.12; N, 13.15.
C33H61N7O2SiSn. Calc.: C, 53.97; H, 8.31; N, 13.35.
3.6. Reaction of 4 with H2O
The procedure for complex 5 was followed with
complex 4 (0.15 g, 0.2 mmol) and H2O (0.0037 g, 0.2
mmol) to give 6 (0.13 g, 92%).
3.8.2. Reaction with dimethylsulfoxide
A solution of 1 (0.4 g, 0.66 mmol), or 2 (0.43 g, 0.66
mmol), in 20 ml of benzene was treated with (0.55 g, 1.9
mmol) of dimethylsulfoxide. The mixture was refluxed
for 2 h. The volatiles were removed in vacuo and the
crude product was crystallized from pentane (ca. 20 ml).
9 (0.34 g, 79%); 10 (0.35 g, 80%).
Complex 6: m.p. 143–144°C. 119Sn{1H}-NMR (C6D6):
1
−485.4. H-NMR (C6D6): 0.28 (s, 9H, SiMe), 2.14 (s,
24H, NMe), 2.21 (s, 12H, NMe), 3.38 (s, 4H, CH2), 3.54
(s, 8H, CH2), 7.22 (s, 4H, C6H2). MS: m/z=753 [M–
3Me]+. IR (C6H6, cm−1): wOH, wNH=3330–3442. Anal.
Found: C, 52.58; H, 8.26; N, 12.89. C33H63N7O3SiSn.
Calc.: C, 52.68; H, 8.38; N, 13.04.
3.8.3. Reaction with pyridine N-oxide
A mixture of 1 (0.4 g, 0.66 mmol), or 2 (0.43 g, 0.66
mmol), and pyridine N-oxide (0.06 g, 0.66 mmol) in 20
ml of benzene was refluxed for 2 h. The volatile was
removed in vacuo. The crude product was crystallized
from pentane (ca. 20 ml). 9 (0.35 g, 85%); 10 (0.35 g,
80%).
3.7. Reaction of 4 with methanol
To a solution of 4 (0.08 g, 0.12 mmol) in 10 ml of
benzene was added an excess of MeOH (0.008 g, 0.25

J. Barrau et al. / Journal of Organometallic Chemistry 570 (1998) 163–174
171
3.9. Reaction of 1 with sulfur
of the formed sulfur 30 ml of pentane was added;
filtration and dried in vacuo afforded the complex 14
(0.41 g, 90%).
A solution of 1 (0.81 g, 1.34 mmol) in 20 ml of benzene
was added to a stirred suspension of sulfur (0.04 g, 1.34
mmol) in 10 ml of benzene. The mixture was refluxed for
3 h. Concentration in vacuo afforded the crude product
which was recrystallized from toluene/pentane (1/1, 20
ml) at −30°C. Filtration gave 11 (0.47 g, 55%).
1
Complex 14: m.p. 133–135°C. H-NMR (C6D6): 1.34
(s, 9H, t-Bu), 1.54 (s, 9H, t-Bu) 1.90 (s, 3H, NMe), 2.07
(s, 3H, NMe), 2.18 (s, 12H, NMe), 2.76 (s, 6H, NMe),
2.23 (s, 6H, NMe), 2.60 (s, 3H, NMe), 2.71 (s, 3H, NMe),
3.13 and 3.61 (AB system, 2H, JAB=12 Hz), 3.94 (s, 4H,
CH2), 3.51 (s, 2H, CH2), 3.54 (s, 2H, CH2), 4.03 and 4.65
(AB system, 2H, JAB=12 Hz), 6.81 and 7.58 (dd, 4H,
C6H2), 6.9 (d, 1H, JHH=2.4 Hz), 7.23 (d, 1H, JHH=2.4
Hz). 13C-NMR (C6D6): 30.10 (+), 32.32 (+), 34.59
(Cquat), 35.18 (Cquat), 44.01 (+), 47.09 (+), 59.06 (−),
64.05 (−), 109.6 (+), 111.9 (+), 127.73 (Cquat), 132.1
(+), 132.5 (Cquat), 139.0 (Cquat), 146.9 (Cquat), 151.2
(Cquat), 159.01 (Cquat), 159.1 (Cquat). MS: m/z=822
Complex 11: m.p. 120−121°C. 1H-NMR (C6D6): 2.13
(s, 24H, NMe), 2.18 (s, 12H, NMe), 3.35 (s, 4H, CH2),
3.55 (s, 8H, CH2), 7.22 (s, 4H, C6H2). 13C-NMR (C6D6):
44.87 (+), 45.42 (+), 60.34 (−), 64.45 (−), 127.57
(Cquat), 129.36 (+), 130.07 (Cquat), 150.8 (Cquat). MS:
m/z=634 [M]+ . Anal. Found: C, 56.75; H, 8.04; N,
’
13.09. C30H52N6O2SGe. Calc.: C, 56.91; H, 8.22; N,
13.28.
[M]+ . Anal. Found: C, 64.22; H, 8.71; N, 10.12.
’
3.10. Reaction of 11 with H2O
C44H72O4N6Ge. Calc.: C, 64.34; H, 8.77; N, 10.23.
To a solution of 11 (0.09 g, 0.14 mmol) in 10 ml of
benzene was added (0.002 g, 0.1 mmol) of water. Imme-
diately, the color of the reaction mixture changed. The
solvent was removed in vacuo. Crystallization from
pentane (ca. 10 ml) afforded 12 as orange crystals (0.08
g, 98%).
3.13. Reaction of 1 with selenium
A solution of 1 (0.97 g 1.6 mmol) in 20 ml of benzene
was added to a stirred suspension of selenium (0.12 g, 1.6
mmol) in 10 ml of benzene. The mixture was refluxed for
3 h and the solvent removed by evaporation under
reduced pressure. The resulting solid product, 15, was
purified by crystallization from toluene/pentane (1/1, 20
ml) at −30°C. Yield: 0.65 g, 60%.
1
Complex 12: m.p. 104–105°C. H-NMR (C6D6): 2.07
(s, 24H, NMe), 2.12 (s, 12H, NMe), 3.32 (s, 4H, CH2),
3.49 (s, 8H, CH2), 7.19 (s, 4H, C6H2). MS: m/z=635
[M–OH]+. IR (C6H6, cm−1): wOH, SH=3274; 2650.
Anal. Found: C, 55.17; H, 8.21; N, 12.76.
C30H54N6O3SGe. Calc.: C, 55.33; H, 8.30; N, 12.91.
1
Complex 15: m.p. 135–136°C. H-NMR (C6D6): 2.11
(s, 24 H, NMe), 2.14 (s, 12 H, NMe), 3.32 (s, 4H, CH2),
3,54 (s, 8H, CH2), 7,27 (s, 4H, C6H2). 13C-NMR (C6D6):
44.92 (+), 45.68 (+), 60.66 (−), 64.71 (−), 127.83
(Cquat), 129.45 (+), 130.34 (Cquat), 151.12 (Cquat). MS:
3.11. Reaction of 11 with methanol
m/z=680 [M]+ . Anal. Found: C, 52.75; H, 7.52; N,
’
A solution of methanol (0.012 g, 0.38 mmol) in 5 ml
of benzene was added dropwise to a solution of 11 (0.13
g, 0.2 mmol) in 10 ml of benzene. The reaction mixture
was stirred for a further 30 min and the volatile removed
in vacuo. Crystallization from pentane (ca. 10 ml) and
filtration gave 13 (0.11 g, 81%).
12.26. C30H52N6O2SeGe. Calc.: C, 52.97; H, 7.65; N,
12.36.
3.14. Reaction of 15 with H2O
H2O (0.002 g, 0.14 mmol) was added to a solution of
15 (0.1 g, 0.14 mmol) in 10 ml of benzene. Immediately,
the mixture reaction turned color. The solvent was
evaporated in vacuo, the residue was extracted with
pentane (ca. 10 ml) and cooled (−30°C) to give 16 as
yellow crystals (0.11 g, 94%).
1
Complex 13: m.p. 98–100°C. H-NMR (C6D6): 2.05
(s, 24H, NMe), 2.19 (s, 12H, NMe), 3.02 (s, 3H, OMe),
3.36 (s, 4H, CH2), 3.52 (s, 8H, CH2), 7.16 (s, 4H, C6H2).
13C-NMR (C6D6): 44.43 (+), 45.31 (+), 51.54 (+),
60.26 (−), 64.32 (−), 127.46 (Cquat), 129.28 (+), 130.11
(Cquat), 150.05 (Cquat). MS: m/z=635 [M–OMe]+. IR
(C6H6, cm−1): wSH=2650. Anal. Found: C, 55.81; H,
8.36; N, 12.91. C31H56N6O3SGe. Calc.: C, 55.97; H, 8.43;
N, 12.64.
1
Complex 16: m.p. 123–124°C. H-NMR (C6D6): 2.04
(s, 24 H, NMe), 2.11 (s, 12 H, NMe), 3.31 (s, 4H, CH2),
3,48 (s, 8H, CH2), 7,18 (s, 4H, C6H2). MS: m/z=681
[M–OH]+. IR (C6H6, cm−1): wOH, SeH=3330; 2570.
Anal. Found: C, 51.44; H, 7.67; N, 11.91.
C30H54N6O3GeSe. Calc.: C, 51.61; H, 7.74; N, 12.04.
3.12. Reaction of 11 with 3,5-di-tert-butyl-1,2-quinone
A solution of 11 (0.36 g, 0.56 mmol) in 20 ml of
benzene was added to a solution of 3,5-di-tert-butyl-1,2-
quinone (0.12 g, 0.56 mmol) in 15 ml of benzene. The
reaction mixture was stirred for 1 h at r.t. After filtration
3.15. Reaction of 15 with methanol
A solution of MeOH (0.009 g, 0.28 mmol) in 5 ml of
benzene was added to a solution of 15 (0.1 g, 0.14 mmol)

172
J. Barrau et al. / Journal of Organometallic Chemistry 570 (1998) 163–174
3.19. (ArO)2SnꢀFe(CO)4 (19)
in 10 ml of benzene. The solution was stirred for 30
min. The volatile materials were removed under re-
duced pressure, and the residue was crystallized in
pentane (ca. 10 ml). Filtration and dried in vacuo
afforded 17 (0.9 g, 90%).
Using the same operating conditions as in the preced-
ing preparation, 19 was obtained from (ArO)2Sn (0.27
g, 0.42 mmol) and Fe(CO)5 (0.08 g, 0.42 mmol). Yield:
0.29 g, 85%.
1
Complex 17: m.p. 112–113°C. H-NMR (C6D6): 2.04
Complex 19: m.p. 110–112°C. 119Sn{1H}-NMR
(s, 24H, NMe) 2.17 (s, 12H, NMe), 3.01 (s, 3H, OMe),
3,34 (s, 4H, CH2), 3.49 (s, 8H, CH2), 7.17 (s, 4H, C6H2).
13C-NMR (C6D6): 44.47 (+), 45.49 (+), 51.50 (+),
60.31 (−), 64.43 (−), 127.47 (Cquat), 129.33 (+),
130.17 (Cquat), 150.12 (Cquat). MS: m/z=681 [M–
OMe]+. IR (C6H6, cm−1): wSeH=2570. Anal. Found:
C, 52.12; H, 7.80; N, 11.67. C31H56N6O3GeSe. Calc.: C,
52.28; H, 7.80; N, 11.67.
(C6D6): −225.9 (1JSnFe=1338 Hz). H-NMR (C6D6):
1
2.18 (s, 12H, NMe), 2.24 (s, 24H, NMe), 3,26 (s, 4H,
CH2), 3.49 (s, 8H, CH2), 7.24 (s, 4H, C6H2). 13C-NMR
(C6D6): 45.09 (+), 45.72 (+), 60.23 (−), 64.06 (−),
127.65 (Cquat), 128.66 (+), 130.39 (Cquat), 157.91
(Cquat), 157.91 (C–O), 216.93 (CꢀO), 218.76 (CꢀO).
MS: m/z=732 [M–3CO]+. IR (C6H6, cm−1): wCꢀO
=
2001, 1946, 1893. Anal. Found: C, 50.02; H, 6.26; N,
10.26. C34H52N6O6FeSn. Calc.: C, 50.09; H, 6.38; N,
10.31.
3.16. Reaction of 15 with 3,5-di-tert-butyl-1,2-quinone
Complex 15 (0.30 g, 0.44 mmol) in benzene (20 ml)
was added to 3,5-di-tert-butyl-1,2-quinone (0.10 g, 0.44
mmol) in benzene (10 ml). The mixture was stirred at
r.t. for 1 h. A red precipitate of selenium appeared
which was eliminated by filtration. Addition of 50 ml of
pentane to the filtrate, filtration and dried in vacuo
gave 14 as yellow crystals (0.33 g, 92%).
3.20. (ArO)2GeꢀW(CO)5 (20)
Using the same operating conditions as in the preced-
ing preparation, 20 was obtained from (ArO)2Ge (0.20
g, 0.34 mmol) and W(CO)6 (0.12 g, 0.34 mmol). Yield:
0.25 g, 82%.
1
Complex 20: m.p. 193–195°C. H-NMR (C6D6): 2.07
(s, 12H, NMe), 2.19 (s, 24H, NMe), 3.36 (s, 4H, CH2),
3.53 (s, 8H, CH2), 7.23 (s, 4H, C6H2). 13C-NMR
(C6D6): 44.79 (+), 45.39 (+), 60.28 (−), 64.02 (−),
127.07 (Cquat), 128.60 (+), 129.37 (Cquat), 157.04 (C–
O), 197.15 (CꢀO), 200.05 (CꢀO). MS: m/z=896 [M–
3.17. Reaction of 15 with sulfur
Complex 15 (0.58 g, 0.96 mmol) in benzene (25 ml)
was added to a suspension of sulfur (0.07 g, 0.96 mmol)
in benzene (10 ml). The mixture was refluxed for 3 h. A
black precipitate of selenium appeared. Filtration and
evaporation of the filtrate provided a yellow powder.
Crystallization from pentane/toluene (1/1, 50 ml) at
−30°C afforded 11 as a yellow powder (0.54 g, 90%).
CO]+ . IR (C6H6, cm−1): wCꢀO=1981, 1948, 1867.
’
Anal. Found: C, 45.32; H, 5.56; N, 8.87.
C35H52N6O7WGe. Calc.: C, 45.43; H, 5.62; N, 9.08.
3.21. (ArO)2SnꢀW(CO)5 (21)
3.18. (ArO)2GeꢀFe(CO)4 (18)
In a similar way the reaction of (ArO)2Sn (0.22 g,
0.34 mmol) with W(CO)6 (0.12 g, 0.34 mmol) afforded
21 (0.28 g, 87%).
A solution of Fe(CO)5 (0.08 g, 0.42 mmol) in 80 ml
of THF was irradiated for 1.5 h. CO was eliminated by
bubbling of nitrogen in the reaction mixture during 15
min, then (ArO)2Ge (0.27 g, 0.42 mmol) in THF (20 ml)
was added. The solution turned dark maroon. After
stirring at r.t. for 1 h the volatile materials were re-
moved under reduced pressure. The residual solid was
recrystallized from pentane (ca. 80 ml). Filtration gave
18 (0.25 g, 79%).
Complex 21: m.p. 206–208°C. 119Sn{1H}-NMR
1
(C6D6): −391.2 (1JSnw=1010 Hz). H-NMR (C6D6):
2.04 (s, 12H, NMe), 2.18 (s, 24H, NMe), 3,35 (s, 4H,
CH2), 3.51 (s, 8H, CH2), 7.22 (s, 4H, C6H2). 13C-NMR
(C6D6): 44.72 (+), 45.32 (+), 60.28 (−), 63.97 (−),
127.60 (Cquat), 128.29 (+), 130.57 (Cquat), 157.65 (C–
O), 213.77 (CꢀO), 215.53 (CꢀO). MS: m/z=942 [M–
CO]+. IR (C6H6, cm−1): wCꢀO=1974, 1933, 1859.
Anal. Found: C, 43.18; H, 5.16; N, 8.49.
C35H52N6O7WSn. Calc.: C, 43.27; H, 5.36; N, 8.65.
1
Complex 18: m.p. 105–107°C. H-NMR (C6D6): 2.07
(s, 12H, NMe), 2.19 (s, 24H, NMe), 3,36 (s, 4H, CH2),
3.54 (s, 8H, CH2), 7.15 (s, 4H, C6H2). 13C-NMR
(C6D6): 44.96 (+), 45.49 (+), 60.33 (−), 64.46 (−),
127.07 (Cquat), 128.60 (+), 129.37 (Cquat), 157.42 (C–
O), 211.30 (CꢀO), 214.60 (CꢀO). MS: m/z=686 [M–
3CO]+. IR (C6H6, cm−1): wCꢀO=1984, 1968, 1887.
Anal. Found: C, 53.02; H, 6.61; N, 10.89.
C34H52N6O6FeGe. Calc.: C, 53.09; H, 6.76; N, 10.93.
3.22. (ArO)2GeꢀCr(CO)5 (22)
Using the same operating conditions as in the preced-
ing preparation, 22 was obtained from (ArO)2Ge (0.28
g, 0.48 mmol) and Cr(CO)6 (0.10 g, 0.48 mmol). Yield:
0.25 g, 82%.

J. Barrau et al. / Journal of Organometallic Chemistry 570 (1998) 163–174
173
Complex 22: m.p. 138−140°C. 1H-NMR (C6D6):
ppm): 8.72, JPPt=3400 Hz; MS: m/z=1321 [M+1]+
’
and of a compound whose nature is still obscure (31P-
NMR (C6D6; d ppm): 53.27, JPPt=4800 Hz)]. All at-
tempts of separation of these products by
recrystallization from various solvents (toluene/diethyl
ether/pentane) at −20°C failed.
2.06 (s, 12H, NMe), 2.18 (s, 24H, NMe), 3.34 (s, 4H,
CH2), 3.51 (s, 8H, CH2), 7.22 (s, 4H, C6H2). 13C-NMR
(C6D6): 44.71 (+), 45.36 (+), 60.18 (−), 63.95 (−),
126.92 (Cquat), 128.33 (+), 129.05 (Cquat), 157.18 (C–
O), 218.40 (CꢀO), 221.10 (CꢀO). MS: m/z=766 [M–
CO]+ . IR (C6H6, cm−1): wCꢀO=2092, 1954, 1914.
’
Anal. Found: C, 52.71; H, 6.43; N, 10.38.
C35H52N6O7CrGe. Calc.: C, 52.99; H, 6.56; N, 10.59.
References
[1] P. Jutzi, Angew. Chem. Int. Ed. Engl. 14 (1975) 232.
[2] L.E. Gusel’Nikov, N.S. Nametkin, Chem. Rev. 79 (1979) 529.
[3] W. Kutzelnigg, Angew. Chem. Int. Ed. Engl. 23 (1984) 272.
[4] K. Seppelt, Angew. Chem. Int. Ed. Engl. 30 (1991) 361.
[5] J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry:
Principles of Structure and Reactivity, 4th ed., Harper Collins,
New York, 1993, p. 865.
[6] (a) R. West, M.J. Fink, J. Michl, Science 214 (1981) 1343. (b) R.
West, Pure Appl. Chem. 56 (1984) 163. (c) R. West, Angew.
Chem. Int. Ed. Engl. 26 (1987) 1201.
3.23. (ArO)2SnꢀCr(CO)5 (23)
In a similar way the reaction of (ArO)2Sn (0.31 g,
0.48 mmol) with W(CO)6 (0.10 g, 0.48 mmol), afforded
23 (0.35 g, 88%). 119Sn{1H}-NMR (C6D6): −213.3.
1H-NMR (C6D6): 2. 05 (s, 12H, NMe), 2.19 (s, 24H,
NMe), 3.34 (s, 4H, CH2), 3.50 (s, 8H, CH2), 7.21 (s,
4H, C6H2). 13C-NMR (C6D6): 44.87 (+), 45.38 (+),
60.29 (−), 64.10 (−), 127.48 (Cquat), 128.08 (+),
[7] T. Tsumuraya, S.A. Batcheller, S. Masamune, Angew. Chem.
Int. Ed. Engl. 30 (1991) 902.
130.15 (Cquat), 157.96 (C–O), 218.39 (CꢀO), 223.56
(CꢀO). MS: m/z=812 [M–CO]+ . IR (C6H6, cm− ):
1
’
[8] (a) N. Tokitoh, H. Suzuki, R. Okazaki, K. Ogawa, J. Am.
Chem. Soc. 115 (1993) 10428. (b) H. Suzuki, N. Tokitoh, R.
Okazaki, et al., Organometallics 14 (1995) 1016. (c) H. Suzuki,
N. Tokitoh, R. Okazaki, Bull. Chem. Soc. Jpn. 68 (1995) 2471.
[9] G. Raabe, J. Michl, Chem. Rev. 85 (1985) 419.
[10] A.G. Brook, K.M. Baines, Adv. Organomet. Chem. 25 (1986) 1.
[11] R. West, Angew. Chem. Int. Ed. Engl. 26 (1987) 1201.
[12] N. Auner, W. Ziche, R. West, Heteroat. Chem. 2 (1991) 335.
[13] N. Wiberg, J. Organomet. Chem. 273 (1984) 141.
[14] K.M. Baines, W.G. Stibbs, Adv. Organomet. Chem. 39 (1996)
275.
[15] J. Satge´, Adv. Organomet. Chem. 21 (1982) 241.
[16] J. Barrau, J. Escudie´, J. Satge´, Chem. Rev. 90 (1990) 283.
[17] J. Escudie´, C. Couret, H. Ranaivonjatovo, J. Satge´, Coord.
Chem. Rev. 130 (1994) 427.
[18] J. Escudie´, C. Couret, H. Ranaivonjatovo, et al., Main Gr. Met.
Chem. 17, 1–4, 1994, p. 33.
[19] A.H. Cowley, N.C. Norman, Prog. Inorg. Chem. 34 (1986) 1.
[20] A.H. Cowley, Polyhedron 3 (1984) 389.
[21] A. Kandri Rodi, H. Ranaivonjatovo, J. Escudie´, A. Kerbal,
Main Gr. Met. Chem. 19 (4) (1996) 199.
[22] P.G. Harrison, in: G. Wilkinson, R.D. Gillard, J.A. McCleverty
(Eds.), Comprehensive Coordination Chemistry, vol. 3, Perga-
mon Press, New York, 1987, ch. 26.
wCꢀO=2087, 1935, 1889. Anal. Found: C, 49.97; H,
6.02; N, 9.88. C35H52N6O7CrSn. Calc.: C, 50.07; H,
6.20; N, 10.01.
3.24. (ArO)2SnꢀPt(PPh3)2 (24)
A sample of bis(triphenylphosphine)(ethylene)platine
(0.13 g, 0.18 mmol) in 10 ml of benzene was added to
a solution of (ArO)2Sn (0.12 g, 0.18 mmol) in 10 ml of
benzene at r.t. The mixture reaction was ultra-sonicated
for 4 h, the solution turned a brick-red color. Volatiles
were evaporated under reduced pressure, and the
residue was recrystallized from toluene/diethyl ether
(1/1, 20 ml) at −20°C. Filtration gave 24 as orange
crystals (0.22 g, 90%).
Complex 24: m.p. 237–239°C. 119Sn{1H}-NMR
(C6D6): −8.39 (1JSnPt=17901 Hz). 2JSnP=3224 Hz.
31P {1H}-NMR (C6D6): 5.22, JPPt=3211 Hz, JPSn
=
1
2
1
3224 Hz. H-NMR (C6D6): 2.06 (s, 12H, NMe), 2.18 (s,
24 H, NMe), 3.36 (s, 4H, CH2), 3.52 (s, 8H, CH2), 7.18
(s, 4H, C6H2), 7.29–8.12 (m, 30H, C6H5). 13C-NMR
(C6D6): 44.86 (+), 45.40 (+), 60.34 (−), 64.47 (−),
[23] J. Satge´, Pure Appl. Chem. 56 (1984) 137.
[24] J. Satge´, J. Organomet. Chem. 400 (1990) 121.
[25] R. Okazaki, N. Tokitoh, A. Ishii, et al., Phosphorus, Sulfur
Silicon 67 (1992) 49.
[26] D.P. Thompson, P. Boudjouk, J. Chem. Soc. Chem. Commun.
(1987) 1466.
127.60 (Cquat), 128.57 (+), 129.24 (Cquat), 134.25
(Cquat), 152.77 (C–O). MS: m/z=1367 [M+1]+
.
’
Anal. Found: C, 57.77; H, 5.84; N, 5.94.
C66H82N6O2P2SnPt. Calc.: C, 57.93; H, 5.99; N, 6.14.
[27] P. Arya, J. Boyer, F. Carre´, et al., Angew. Chem. Int. Ed. Engl.
28 (1989) 1016.
[28] P. Jutzi, A. Mo¨hrke, A. Mu¨ller, H. Bo¨gge, Angew. Chem. Int.
Ed. Engl. 28 (1989) 1518.
3.25. (ArO)2GeꢀPt(PPh3)2 (25)
[29] J. Barrau, V. Balaji, J. Michl, Organometallics 8 (1989) 2034.
[30] (a) M. Veith, S. Becker, V. Huch, Angew. Chem. Int. Ed. Engl.
28 (1989) 1237. (b) M. Veith, S. Becker, V. Huch, Angew. Chem.
Int. Ed. Engl. 29 (2) (1990) 216. (c) M. Veith, A. Detemple,
Phosphorus, Sulfur Silicon 65 (1992) 17.
[31] (a) N. Tokitoh, T. Matsumoto, K. Manmaru, R. Okazaki, J.
Am. Chem. Soc. 115 (1993) 8855. (b) N. Tokitoh, T. Mat-
sumoto, R. Okazaki, Chem. Lett. (1995) 1087. (c) N. Tokitoh,
An extremely air-sensitive yellow solid, was obtained
in 45% yield, under conditions described above for 24,
from (ArO)2Ge (0.11 g, 0.18 mmol) and
(Ph3P)2Pt·C2H4 (0.13 g, 0.18 mmol). Analysis by 31P-
NMR and mass spectroscopy of this crude material
showed that it was a mixture of 25 [31P-NMR (C6D6; l

174
J. Barrau et al. / Journal of Organometallic Chemistry 570 (1998) 163–174
Ed. Engl. 33 (10)(1994) 1097. (d) R.J.P. Corriu, G.F. Lanneau,
Y. Matsuhashi, K. Shibata, et al., Main Gr. Met. Chem. 17(1–4)
(1994) 55. (d) R. Okazaki, Phosphorus, Sulfur Silicon, 95–96
(1994) 21. (e) T. Matsumoto, K. Kishikawa, N. Tokitoh, R.
Okazaki, Phosphorus, Sulfur Silicon, 93–94 (1994) 177. (f) N.
Tokitoh, M. Saito, R. Okazaki, J. Am. Chem. Soc. 115 (1993)
2065. (g) T. Matsumoto, N. Tokitoh, R. Okazaki, Angew.
Chem. Int. Ed. Engl. 33 (1994) 2316. (h) N. Tokitoh, T. Mat-
sumoto, R. Okazaki, Chem. Lett. (1995) 1087. (i) N. Tokitoh, T.
Matsumoto, R. Okazaki, J. Am. Chem. Soc. 119 (1997) 2337.
C. Priou, Angew. Chem. Int. Ed. Engl. 30 (1991) 1130.
[49] (a) C. Zybill, H. Handwerker, H. Friedrich, Adv. Organomet.
Chem. 36 (1994) 229. (b) C. Zybill, C. Liu, Synlett. (1995) 687.
(c) C. Leis, C. Zybill, J. Lachmann, G. Mu¨ller, Polyhedron
10(11) (1991) 1163.
[50] P.D. Likiss, Chem. Soc. Rev. 24 (1992) 271.
[51] (a) K. Ueno, H. Tobita, H. Ogino, J. Organomet. Chem. 430
(1992) 93. (b) M. Okazaki, H. Tobita, H. Ogino, Chem. Lett. 6
(1996) 477. (c) H. Tobita, K. Ishiyama, Y. Kawano, S. Inomata,
H. Ogino, Organometallics 17 (1998) 789.
[32] (a) M.C. Kuchta, G. Parkin, J. Chem. Soc. Chem. Commun.
(1994) 1351. (b) M.C. Kuchta, G. Parkin, J. Am. Chem. Soc. 116
(1994) 8372. (c) M.C. Kuchta, G. Parkin, J. Chem. Soc. Chem.
Commun. (1996) 1669.
[52] N. Tokitoh, K. Manmaru, R. Okazaki, Organometallics 13
(1994) 167.
[53] T.R. Cundari, M.R. Gordon, J. Phys. Chem. 96 (2) (1992) 631.
[54] (a) H. Handwerker, M. Paul, J. Blu¨mel, C. Zybill, Angew.
Chem. Int. Ed. Engl. 32(9) (1993) 1313. (b) H. Handwerker, C.
Leis, R. Probst, et al., Organometallics 12 (1993) 2162.
[55] M. Veith, O. Recktenwald, Top. Curr. Chem. 104 (1982) 1.
[56] H.P. Abicht, K. Jurkschat, A. Tzschach, K. Peters, E.-M. Peters,
H.G. von Schnering, J. Organomet. Chem. 326 (1987) 357.
[57] L. Angermund, K. Jonas, C. Kru¨ger, J.L. Latten, Y.-H. Tsay, J.
Organomet. Chem. 353 (1988) 17.
[58] (a) M. Weidenbruch, A. Stilter, J. Schlaefke, K. Peters, H.G. von
Schnering, J. Organomet. Chem. 501 (1995) 67. (b) M. Weiden-
bruch, A. Stilter, K. Peters, H.G. von Schnering, Z. Anorg. Allg.
Chem. 622 (1996) 534.
[59] (a) J.T.B.H. Jastrzebski, P.A. van der Schaaf, J. Boersma, G.
van Koten, J. Organomet. Chem. 367 (1989) 55. (b) G. van
Koten, J.T.B.H. Jastrzebski, J.G. Noltes, A.L. Speck, J.C.
Shoone, J. Organomet. Chem. 184 (1978) 233.
[60] R.D. Adams, M.D. Brice, F.A. Cotton, Inorg. Chem. 13 (5)
(1974) 1080.
[61] (a) T.D. Tilley, Acc. Chem. Res. 26 (1993) 22. (b) S.D. Grum-
bine, R.K. Chadha, T.D. Tilley, J. Am. Chem. Soc. 114 (1992)
1518.
[62] K.E. Litz, K. Hendersen, R.W. Gourley, N.M.B. Holl,
Organometallics 14 (1995) 5008.
[63] P.B. Braunstein, V. Huch, C. Stern, M. Veith, J. Chem. Soc.
Chem. Commun. (1996) 2041.
[64] R.S. Simons, C.A. Tessier, Organometallics 15 (1996) 2604.
[65] (a) J. Barrau, G. Rima, T. El Amraoui, Inorg. Chim. Acta (1996)
241. (b) J. Barrau, G. Rima, T. El Amraoui, Organometallics 17
(1998) 607.
[33] G. Ossig, A. Meller, C. Bro¨nneke, O. Mu¨ller, M. Scha¨fer, R.
Herbst-Irmer, Organometallics 16 (1997) 2116.
[34] J.E. Bender IV, M.M. Banaszak Holl, J.W. Kampf,
Organometallics 16 (1997) 2743.
[35] S.R. Foley, C. Bensimon, D. Richeson, J. Am. Chem. Soc. 119
(1997) 10359.
[36] (a) Y. Matsuhashi, N. Tokitoh, R. Okazaki, Organometallics 12
(1993) 2573. (b) N. Kano, N. Tokitoh, R. Okazaki, Chem. Lett.
(1997) 277.
[37] Y. Zhow, D.S. Richeson, J. Am. Chem. Soc. 118 (1996) 10850.
[38] T. Hayashi, H. Yamashita, M. Tanaka, M. Goto, Organometal-
lics 11 (1992) 3227.
[39] (a) K.H. Pannell, J. Cervantes, L. Parkanyi, F. Cervantes Lee,
Organometallics 9 (1990) 859. (b) K.H. Pannell, M.C. Brun, H.
Sharma, K. Jones, S. Sharma, Organometallics 13(4) (1994)
1075.
[40] R.H. Heyn, T.D. Tilley, J. Am. Chem. Soc. 114 (1992) 1917.
[41] W. Finckh, B.Z. Tang, A. Lough, I. Manners, Organometallics
11 (1992) 2904.
[42] M. Ishikawa, A. Naka, S. Okazaki, H. Sakamoto, Organometal-
lics 12 (1993) 87.
[43] E.H. Brooks, R.J. Cross, Organomet. Chem. Rev. A 6 (1970)
227.
[44] W. Petz, Chem. Rev. 86 (1986) 1019.
[45] (a) A. Castel, P. Rivie`re, J. Satge´, M. Ahbala, J. Organomet.
Chem. 331 (1987) 11. (b) A. Castel, P. Rivie`re, J. Satge´, M.
Ahbala, J. Organomet. Chem. 328 (1987) 123.
[46] (a) P. Jutzi, Adv. Organomet. Chem. 26 (1986) 217. (b) P. Jutzi,
B. Hampel, M.B. Hursthouse, A.J. Howes, J. Organomet. Chem.
299 (1986) 19.
[66] M. Rivie`re-Baudet, P. Rivie`re, A. Kallaayoun, J. Satge´, K.
Rauzy, J. Organomet. Chem. 358 (1988) 77.
[67] M. Rivie`re-Baudet, A. More`re, A. Kallaayoun, J. Organomet.
Chem. 443 (1993) 43.
[47] (a) M.F. Lappert, R.S. Rowe, Coord. Chem. Rev. 100 (1990)
267. (b) P.B. Hitchcock, M.F. Lappert, M.J. McGeary,
Organometallics 9 (1990) 884.
[48] (a) B.P.S. Chauhan, R.J.P. Corriu, G.F. Lanneau, et al.,
Organometallics 14 (1995) 1657. (b) R.J.P. Corriu, G. Lanneau,
B.P.S. Chauhan, Organometallics 12 (1993) 2001. (c) F. Carre´,
C. Chuit, R.J.P. Corriu, A. Mehdi, C. Reye´, Angew. Chem. Int.
[68] P. Rivie`re, A. Castel, C. Abdennadher, Phosphorus, Sulfur
Silicon 82 (1993) 181.
[69] P. Rivie`re, M. Rivie`re-Baudet, A. Castel, Main Gr. Met. Chem.
17 (1994) 679.
.
.