Preparation, crystal structure determination and properties of adducts of indium methylene compounds with Group 15 donors
The reaction of InBr with CH 2Br 2 in 1,4-dioxane or acetonitrile yields the corresponding solvate of Br 2InCH 2Br, which on reaction with E(C 6H 5) 3 (E=P, As, Sb) gives the indium(III)-Group 15 dimetallo-methane derivatives, Br 3InCH 2E(C 6H 5) 3. The crystal structures of the two related compound...
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| Published in: | Journal of organometallic chemistry Vol. 603; no. 2; pp. 203 - 212 |
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| Main Authors: | , , , , , , , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
Elsevier B.V
29-05-2000
|
| Subjects: | |
| Online Access: | Get full text |
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| Summary: | The reaction of InBr with CH
2Br
2 in 1,4-dioxane or acetonitrile yields the corresponding solvate of Br
2InCH
2Br, which on reaction with E(C
6H
5)
3 (E=P, As, Sb) gives the indium(III)-Group 15 dimetallo-methane derivatives, Br
3InCH
2E(C
6H
5)
3. The crystal structures of the two related compounds (E=As, Sb) have been determined by X-ray crystallography. For Br
3InCH
2As(C
6H
5)
3, cell constants
a=15.553(7),
b=21.646(8),
c=12.920 (10) Å; space group
Pbca,
Z=8,
R=0.064,
R
w=0.054, and for Br
3InCH
2Sb(C
6H
5)
3,
a=15.439(6) Å,
b=22.016(4)
c=13.138(5) Å; space group
Pbca,
Z=8,
R=0.062,
R
w=0.049. Results are also reported for I
3InCH
2As(C
6H
5)
3 (cell constants
a=12.0122(2),
b=15.8526(3),
c=13.4180(3) Å,
β=109.933(1)°; space group
P2
1/
n
,
Z=4,
R=0.0481,
R
w=0.0431) and Br
3InCH
2N(C
2H
5)
3 (
a=7.362(2),
b=14.700(2),
c=13.049(1) Å,
β=98.90(1)°; space group
P2
1/
n
,
Z=4,
R=0.0418,
R
w=0.0368). The structural results are compared with those for other organoindium ylids with the same general structure Br
3InCH
2L (L=P(C
6H
5)
3; 1,1,3,3,-tetramethyl-2-thiourea;
N,
N,
N′,
N′-tetramethylethanediamine). Semi-empirical quantum mechanical calculations, using the PM3 method, were carried out on the series Br
3InCH
2E(C
6H
5)
3 (E=P, As, Sb), and the calculated structural parameters are compared with the values determined by X-ray crystallography. The presence of an ylid ligand H
2C
δ−
δ+
E(C
6H
5)
3 in the organoindium compounds is confirmed. Mass spectra and thermogravimetric analysis strongly suggest that the thermal decomposition of the compounds occurs via fission of the indiumcarbon bond, leading to the corresponding ylid, which can be trapped by reacting the X
3InCH
2E(C
6H
5)
3 compounds with HBr to produce the onium derivative [CH
3E(C
6H
5)
3]
+ [InX
4]
− (E=P, As; X=Br, I). |
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| ISSN: | 0022-328X 1872-8561 |
| DOI: | 10.1016/S0022-328X(00)00178-9 |