Loading…
Cyanide free contraction of disclosed 1,4-dioxane ring as a route to cobalt bis(dicarbollide) derivatives with short spacer between the boron cage and terminal functional groupIn memory of Professor Kenneth Wade (1932-2014).Electronic supplementary information (ESI) available. See DOI: 10.1039/c5dt01293g
The 1,4-dioxane derivative of cobalt bis(dicarbollide) reacts with dialkylsulfides and triphenylphosphine to give the corresponding sulfonium and phosphonium derivatives [8-L(CH 2 CH 2 O) 2 -3,3′-Co(1,2-C 2 B 9 H 10 )(1′,2′-C 2 B 9 H 11 )] (L = SMe 2 , S(CH 2 CH 2 ) 2 O, PPh 3 ). The treatment of th...
Saved in:
| Main Authors: | , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Online Access: | Get full text |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Summary: | The 1,4-dioxane derivative of cobalt bis(dicarbollide) reacts with dialkylsulfides and triphenylphosphine to give the corresponding sulfonium and phosphonium derivatives [8-L(CH
2
CH
2
O)
2
-3,3′-Co(1,2-C
2
B
9
H
10
)(1′,2′-C
2
B
9
H
11
)] (L = SMe
2
, S(CH
2
CH
2
)
2
O, PPh
3
). The treatment of the triphenylphosphonium derivative with sodium hydroxide results in contraction of the side chain with formation of [8-HOCH
2
CH
2
O-3,3′-Co(1,2-C
2
B
9
H
10
)(1′,2′-C
2
B
9
H
11
)]
−
. The same product was obtained by treatment of the dimethylsulfonium derivative with the poorly nucleophilic base
t
-BuOK, whereas the stronger nucleophiles induce the sulfur demethylation to give [8-MeS(CH
2
CH
2
O)
2
-3,3′-Co(1,2-C
2
B
9
H
10
)(1′,2′-C
2
B
9
H
11
)]
−
. The alcohol was used for the synthesis of a series of other short-spacer functional derivatives [8-XOCH
2
CH
2
O-3,3′-Co(1,2-C
2
B
9
H
10
)(1′,2′-C
2
B
9
H
11
)]
−
(X = NH
2
, SH, N
3
). A similar contraction of the disclosed 1,4-dioxane ring
via
the reactions with SMe
2
and PPh
3
can be used for the synthesis of short-spacer functional derivatives of
nido
-carborane, whereas the 1,4-dioxane derivatives of
closo
-decaborate and
closo
-dodecaborate anions, being stronger electron donors, are more stable and do not react with dimethylsulfide and triphenylphosphine.
The 1,4-dioxane derivative of cobalt bis(dicarbollide) reacts with dialkylsulfides and triphenylphosphine to give the corresponding sulfonium and phosphonium derivatives. |
|---|---|
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c5dt01293g |