Simple entry into N-tert-butyl-iminophosphonamide rare-earth metal alkyl and chlorido complexesCCDC 901055-901056 and 1414805-1414808. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt03721b
In situ protolysis reaction of a highly basic and sterically hindered N , N ′-di- tert -butyl-iminophosphonamide ligand Ph 2 P(&z.dbd;N- t Bu)(NH- t Bu) = (NPN t Bu )H ( 1 ) with equimolar or hemimolar amounts of rare-earth metal tris-alkyls leads to dialkyl [(NPN t Bu )Ln(CH 2 SiMe 3 ) 2 (THF)...
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| Main Authors | , , |
|---|---|
| Format | Journal Article |
| Published |
19.01.2016
|
| Online Access | Get full text |
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| Summary: | In situ
protolysis reaction of a highly basic and sterically hindered
N
,
N
′-di-
tert
-butyl-iminophosphonamide ligand Ph
2
P(&z.dbd;N-
t
Bu)(NH-
t
Bu) = (NPN
t
Bu
)H (
1
) with equimolar or hemimolar amounts of rare-earth metal tris-alkyls leads to dialkyl [(NPN
t
Bu
)Ln(CH
2
SiMe
3
)
2
(THF)
n
] (Ln = Sc,
n
= 0 (
2
), Ln = Y,
n
= 1 (
3
)) and monoalkyl species [(NPN
t
Bu
)
2
Ln(CH
2
SiMe
3
)] (Ln = Y (
4
), Nd (
6
), Sm (
7
)). One-pot reaction of [ScCl
3
(THF)
3
]/
1
/MeLi in 1/2/3 eq. ratio gives [(NPN
t
Bu
)
2
Sc(THF)CH
3
]
5
. Further reaction of
4
with phenylacetylene resulted in the formation of the Y-alkynyl complex [(NPN
t
Bu
)
2
Y(-C&z.tbd;CPh)]
8
. Alkyl abstraction in
2
,
3
and
4
by reaction with [PhNMe
2
H]
+
[B(C
6
F
5
)
4
]
−
resulted in the formation of cationic alkyl complex ion-pairs [(NPN
t
Bu
)Ln(CH
2
SiMe
3
)(THF)
n
]
+
[B(C
6
F
5
)
4
]
−
(Ln = Sc (
9
), Y (
10
)) and [(NPN
t
Bu
)
2
Y(THF)
n
]
+
[B(C
6
F
5
)
4
]
−
11
, as confirmed by NMR data. The reaction of bis-NPN alkyl complexes with CHCl
3
is the simplest and most reliable protocol to synthesize bis-NPN-chlorido complexes [(NPN
t
Bu
)
2
Ln-Cl] (Ln = Sc (
12
), Y (
13
), Nd (
14
), Sm (
15
), Gd (
16
), Tb (
17
), Yb (
18
) and Lu (
19
)), which can become new post-metallocene alternatives to the prominent organolanthanide building blocks [Cp*
2
LnX]. Partial hydrolysis of
12
leads to the formation of the oxido/chlorido-capped trinuclear complex [{(NPN
t
Bu
)Sc(μ
2
-Cl)}
3
(μ
3
-O)(μ
3
-Cl)]
20
. Molecular structures of
4
,
6
,
7
,
13
,
19
and
20
were confirmed by X-ray structure analyses.
New series of rare-earth metal dialkyls [(NPN
t
Bu
)Ln(CH
2
SiMe
3
)
2
(THF)
n
] (Ln = Sc,
n
= 0 (
2
), Ln = Y,
n
= 1 (
3
)) and monoalkyls [(NPN
t
Bu
)
2
Ln(CH
2
SiMe
3
)] (Ln = Y (
4
), Nd (
6
), Sm (
7
)), [(NPN
t
Bu
)
2
Sc(THF)CH
3
] (
5
) are achieved by protolysis of highly basic ligand Ph
2
P(&z.dbd;N-
t
Bu)(NH-
t
Bu) = (NPN
t
Bu
)H (
1
). Further alkyl abstraction, alkyl/Cl exchange reactions and X-ray structure analyses of thus obtained new complexes are presented. |
|---|---|
| Bibliography: | CCDC 901055-901056 and For crystallographic data in CIF or other electronic format see DOI 10.1039/c5dt03721b 1414805-1414808 |
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c5dt03721b |