The reactions of R2Ga-GaR2 and R2In-InR2 [R = CH(SiMe3)2] with protic reagents: Substituent exchange versus cleavage of the element-element bond

Article abstract of DOI:10.1002/(SICI)1099-0682(199803)1998:3<355::AID-EJIC355>3.0.CO;2-H

Tetrakis[bis(trimethylsilyl)methyl]digallane(4) (1) with a Ga-Ga single bond and the corresponding diindane(4) 2 with an In-In single bond were treated with different protic reagents: tert-Butyl alcohol did not react with 1 at all, while phenol gave a mix

Full text of DOI:10.1002/(SICI)1099-0682(199803)1998:3<355::AID-EJIC355>3.0.CO;2-H

FULL PAPER
؊
؊
؍
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Tetrakis[bis(trimethylsilyl)methyl]digallane(4) (1) with
a
chelating acid dibenzoylmethane reacted by means of a sub-
GaϪGa single bond and the corresponding diindane(4) 2 stituent exchange, with the release of two equiv. of bis(tri-
with an InϪIn single bond were treated with different protic
reagents: tert-Butyl alcohol did not react with 1 at all, while
methylsilyl)methane for each formula unit of 1, to form 9, in
which the GaϪGa bond is retained and each chelating 1,3-
phenol gave a mixture of unknown products, which could diphenyl-1,3-propanedionato ligand is in a terminal position
not be separated. The more acidic pentafluorophenol did not bonded to only one Ga atom, in more than 80% yield. The
react as an acid, but CϪF bonds were cleaved to form almost
quantitatively the dimer (R2GaF)2 5, which was characterized
GaϪGa bond is shortened [244.1(1) pm] compared to that in
the starting compound tetraalkyldigallane(4) 1. The InϪIn
by a crystal-structure determination. Water and 1 yielded the bond of diindane(4) 2 is, however, cleaved in a similar reac-
dimeric dialkylgallium hydroxide 6. The GaϪGa bond was
also cleaved by the reaction of 1 with durylthiophenol (du-
tion with dibenzoylmethane, and only the fragmentation pro-
duct dialkyl(1,3-diphenyl-1,3-propanedionato)indium 10
ryl = 2,3,5,6-tetramethylphenyl), which gave two main prod- could be isolated.
ucts: R2Ga(SDuryl) 7 and RGa(SDuryl)2 8. In contrast, the
°
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Ј
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tert
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°
δ ϭ
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δ ϭ
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δ ϭ Ϫ
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n
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°
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°
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°
Ϫ
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α
δ ϭ Ϫ
δ ϭ
δ ϭ
π
δ ϭ
C
C
δ ϭ
H
δ ϭ Ϫ
H
δ ϭ
C
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ϭ
P
°
°
°
°
µ
°
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i
Ϫ
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Ϫ
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D
Ϫ
°
Ϫ
Ϫ
Ј
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ЈϪ
Ϫ
ЈϪ
Ϫ
ЈϪ
Ј Ϫx Ϫy
Ϫ
Ϫ z
trans
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FULL PAPER
δ
δ
ρ
ν
ν
ν
ν
δ
Ϫ
Synthesis
of
Dialkylbis(µ-1,3-diphenyl-1,3-propanedionato-
O,OЈ)digallium
n
Ϫ
°
ϩ
n-
Deutsche Forschungsgemeinschaft
Ϫ
°
Fonds der Chemischen Industrie
n
Ϫ
°
General:
n
Ϫ
°
Ϫ
δ ϭ
n
o
p
m
Ϫ
Ϫ
Ϫ
δ ϭ
tert
Ϫ
Ϫ
ν ϭ
ϩ
Synthesis of (R2GaF)2
n
δ
ν
ν
δ
ρ
n
ν
ν
Ϫ
°
ν
ν
°
Ϫ
δ
Ϫ
n
λ
ε ϭ
δ ϭ
Ϫ
ϩ
Ϫ
m/z
δ ϭ
δ ϭ Ϫ
Ϫ
Ϫ
Ϫ
ν ϭ
Ϫ
Ϫ
δ
δ
ρ
ν
ν
δ
ν
ν
Reaction of Diindane(4) with Dibenzoylmethane:
ν
ν
n
Ϫ
Ϫ
°
Ϫ
n
Reaction of Digallane(4) with Water:
n-
µ
Ϫ
°
n
Ϫ
°
Reaction of Digallane(4) with Durylthiol:
n-
Synthesis of Dialkyl(1,3-diphenyl-1,3-propanedionato-O,OЈ)ind-
ium
Ϫ
°

n
Ϫ
°
n-
n
n
Ϫ
°
Ϫ
°
Ϫ
δ ϭ
δ ϭ
o
Ϫ
Ϫ
Ϫ
δ ϭ
°
Ϫ
Ϫ
Ϫ
δ ϭ
ν ϭ
Ϫ
Ϫ
δ ϭ
ν
ν
δ
Ϫ
ν ϭ
ν
ν
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Chem. Ber.
130
Ϫ
δ
ρ
ν
ν
Chem. Ber.
125
Ϫ
ν
ν
δ
Ϫ
Ϫ
Chem. Ber.
130
Ϫ
Inorg. Chim. Acta
Crystal-Structure Determinations:
249
Ϫ
Schwingungsfrequenzen I Ϫ
Hauptgruppenelemente
Z. Anorg. Allg. Chem.
612
105
Ϫ
Ϫ
Angew. Chem.
Angew. Chem. Int. Ed. Engl.
32
Ϫ
Ϫ
Ϫ
Inorg. Chem.
35
Ϫ
Z. Anorg. Allg. Chem.
621
Ϫ
Organometallics
Z. Anorg.
15
Ϫ
Allg. Chem.
Chem. Ber.
619
129
Ϫ
Ϫ
Ϫ
Polyhedron
Chem. Rev.
16
158
Ϫ
Ϫ
Ϫ
Coord.
J. Am. Chem. Soc.
J. Organomet. Chem.
119
Ϫ
493
Ϫ
J. Coord. Chem.
30
Ϫ
Chem.
ibid.
P
P
Ber.
101
Ϫ
Z
T
d
101
Ϫ
Angew. Chem.
79
Ϫ
Angew. Chem. Int. Ed.
J. Am. Chem. Soc.
Engl.
84
6
Ϫ
a
Ϫ
b
c
Angew. Chem.
Angew. Chem. Int. Ed. Engl. 32
Angew. Chem.
Angew. Chem. Int. Ed. Engl. 32
105
105
Ϫ
α °
β °
γ °
V
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
J. Solid State Chem.
Angew. Chem.
µ
61
Ϫ
108
ϫ
ϫ
ϫ
ϫ
Ϫ
Angew. Chem. Int. Ed. Engl.
35
Ϫ
Z. Naturforsch., B: Chem. Sci.
Kα
49
Ϫ
° Յ Θ Յ
Յ h Յ
°
° Յ Θ Յ
Ϫ
Ϫ
Ϫ
ω
°
Acta Crystallogr. B
35
Ϫ
Ϫ
Ϫ
Ϫ
ω
Յ h Յ
Յ k Յ
Յ l Յ
Acta Crystallogr. B
Z. Naturforsch., B: Chem. Sci.
32
Ϫ
Յ k Յ
Յ l Յ
45
Ϫ
Soc.
J. Am. Chem.
Angew. Chem. 107
117
Ϫ
Ϫ
Angew. Chem. Int. Ed. Engl.
34
Ϫ
F
σ F
J. Am. Chem. Soc.
117
Ϫ
R ϭ ΣʈF ͉ Ϫ ͉F ʈ Σ͉F ͉
Organometallics
15
Ϫ
F
σ F
wR ϭ Σw F ϪF
Σw F
J. Chem. Soc., Chem. Commun.
Ϫ
J. Am.
Chem. Soc.
118
Ϫ
J. Organomet. Chem.
524
Ϫ
Acta Crystallogr. B
30
Ϫ
Ϫ
Ϫ
Inorg. Chim. Acta
217
Ϫ
Ϫ
International Tables for Crystallography, Space
Group Symmetry
Ϫ
Ϫ
SHELXTL-Plus REL. 4.1
Z. Naturforsch., B: Chem. Sci.
43
Ϫ
SHELXL-
J. Organomet. Chem.
93, Program for the Refinement of Structures
364
Ϫ
J. Organomet. Chem
368
Ϫ
Z. Anorg. Allg. Chem. 623
Chem. Ber.
Ϫ
129
Ϫ
Ϫ
Ϫ
Eur. J. Inorg. Chem.
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