Loading…
Chemistry of group 5 metallaboranes with heterocyclic thiol ligands: a combined experimental and theoretical study
Thermolysis of [(Cp*Nb) 2 (B 2 H 6 ) 2 ], 1b (Cp* = η 5 -C 5 Me 5 ), with 2-mercaptobenzothiazole, C 6 H 4 NSCSH (MBT), and 2-mercaptobenzoxazole, C 6 H 4 NOCSH (MBO), yielded hydrogen substituted compounds 2 and 3 with a general formula [(Cp*Nb) 2 (B 2 H 6 )(B 2 H 5 L)] ( 2 : L = C 6 H 4 NSCS and 3...
Saved in:
| Published in: | Dalton transactions : an international journal of inorganic chemistry 2021-03, Vol.5 (11), p.436-444 |
|---|---|
| Main Authors: | , , , , , |
| Format: | Article |
| Language: | English |
| Subjects: | |
| Citations: | Items that this one cites Items that cite this one |
| Online Access: | Get full text |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Summary: | Thermolysis of [(Cp*Nb)
2
(B
2
H
6
)
2
],
1b
(Cp* = η
5
-C
5
Me
5
), with 2-mercaptobenzothiazole, C
6
H
4
NSCSH (MBT), and 2-mercaptobenzoxazole, C
6
H
4
NOCSH (MBO), yielded hydrogen substituted compounds
2
and
3
with a general formula [(Cp*Nb)
2
(B
2
H
6
)(B
2
H
5
L)] (
2
: L = C
6
H
4
NSCS and
3
: L = C
6
H
4
NOCS). A similar reaction of
1b
with Ph
2
Se
2
yielded the monosubstituted derivative [(Cp*Nb)
2
(B
2
H
6
){B
2
H
5
(PhSe)}],
4
. All further efforts towards persubstitution of
1b
under various drastic conditions were unfruitful. In parallel, in an effort to find a better synthetic route to the known Ta-aziridine complex [Cp*TaBH(C
7
H
4
NS
2
)CH
2
S
2
NC
6
H
4
], Cp*TaCl
4
was treated with a 2-mercaptobenzothiazolyl-based borate ligand Na[H
2
B(C
6
H
4
NSCS)
2
]. Surprisingly, the reaction led to the formation of the half-sandwich trichloroaryltantalum(
v
) complex [Cp*TaCl
3
{κ
2
-N,S-C
6
H
4
NSCS}],
5
, containing a heterocyclic thiol ligand. Using an alternative method complex
5
was isolated in good yield when Cp*TaCl
4
was treated with the potassium salt of 2-mercaptobenzothiazole K[C
6
H
4
NSCS]. All the compounds were characterized by
1
H,
11
B{
1
H}, and
13
C{
1
H} NMR spectroscopy, and their structures were unequivocally established by crystallographic analysis.
New synthetic methods for the Ta-aziridine species [Cp*TaBH(C
7
H
4
NS
2
)CH
2
S
2
NC
6
H
4
] and the 16-electron half-sandwich complex [Cp*TaCl
3
{κ
2
-N,S-C
6
H
4
SNCS}] having κ
2
-N,S coordination mode have been developed. |
|---|---|
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/d0dt04362a |