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Synthesis and characterization of five-coordinate, 16-electron RuII complexes supported by tridentate bis(phosphino)silyl ligationElectronic supplementary information (ESI) available: Variable temperature NMR data for 9 and crystallographic data for 3, 4, 5, 9 and 11 (CIF). CCDC 1029415-1029419. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6dt01869f
The synthesis of 16-electron complexes of the type (Cy-PSiP)RuX(L) (Cy-PSiP = κ 3 -(2-Cy 2 P C 6 H 4 ) 2 Si Me) is reported. Treatment of (Cy-PSiP)H with one equiv. RuCl 2 (PPh 3 ) 3 in the presence of Et 3 N afforded a mixture of (Cy-PSiP)RuCl(PPh 3 ) ( 1 ) and [(Cy-PSiP)RuCl] 2 ( 2 ), which exists...
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| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Online Access: | Get full text |
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| Summary: | The synthesis of 16-electron complexes of the type (Cy-PSiP)RuX(L) (Cy-PSiP = κ
3
-(2-Cy
2
P
C
6
H
4
)
2
Si
Me) is reported. Treatment of (Cy-PSiP)H with one equiv. RuCl
2
(PPh
3
)
3
in the presence of Et
3
N afforded a mixture of (Cy-PSiP)RuCl(PPh
3
) (
1
) and [(Cy-PSiP)RuCl]
2
(
2
), which exists in a temperature-dependent equilibrium process involving reversible dissociation of PPh
3
from
1
to form
2
. While treatment of this equilibrium mixture with PMe
3
afforded (Cy-PSiP)RuCl(PMe
3
) (
3
) cleanly, this product was more straightforwardly prepared by the addition of PMe
3
to
2
(97% yield). Attempts to form an alkyl complex of the type (Cy-PSiP)RuMe(PMe
3
)
via
treatment of
3
with MeMgBr led to the dehydrogenation and cyclometalation of a cyclohexyl phosphino group to give the isolable 18-electron complex [MeSi(C
6
H
4
PCy
2
)(C
6
H
4
PCy(η
3
-C
6
H
8
))]RuPMe
3
(
4
, 78% yield). The hydrido complex (Cy-PSiP)RuH(PMe
3
) (
5
) was identified as a minor by-product in this dehydrogenative process. Whereas simple 16-electron alkyl complexes of the type (Cy-PSiP)RuR(PMe
3
) remained elusive, the isolable allyl complex (Cy-PSiP)Ru(η
3
-C
3
H
5
) (
9
) was successfully prepared from
2
and (C
3
H
5
)MgCl (79% yield). Treatment of
3
with Me
3
SiN
3
or NaN
3
did not generate a five-coordinate azido species. However, the putative dinuclear complex [(Cy-PSiP)RuN
3
]
2
(
10
) was observed to react with one equiv. of PMe
3
to afford the isolable five-coordinate azido complex (Cy-PSiP)Ru(N
3
)(PMe
3
) (
11
; 94% yield). Crystallographic data for
3
,
4
,
5
,
9
and
11
are presented.
New electronically and coordinatively unsaturated complexes of the type (Cy-PSiP)RuX(L) (Cy-PSiP = κ
3
-(2-Cy
2
P
C
6
H
4
)
2
Si
Me) are reported, including examples of 16-electron allyl and azido Ru species. |
|---|---|
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c6dt01869f |