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Syntheses of highly unsaturated isocyanides via organometallic pathwaysCCDC reference numbers 179717179718 and 836248836250. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c1dt11382h
The carbon carbon coupling reaction by nucleophilic attack of (CO) 5 Cr(CNCF&z.dbd;CF 2 ) 1 by lithium or Grignard compounds 2ai yields the isocyanide complexes (CO) 5 Cr(CNCF&z.dbd;CFR) 3ai ( a R = CH&z.dbd;CH 2 , b R = CH&z.dbd;CF 2 , c R = C&z.tbd;CH, d R = C&z.tbd;CSiMe 3...
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| Format: | Article |
| Language: | English |
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| Summary: | The carbon carbon coupling reaction by nucleophilic attack of (CO)
5
Cr(CNCF&z.dbd;CF
2
)
1
by lithium or Grignard compounds
2ai
yields the isocyanide complexes (CO)
5
Cr(CNCF&z.dbd;CFR)
3ai
(
a
R = CH&z.dbd;CH
2
,
b
R = CH&z.dbd;CF
2
,
c
R = C&z.tbd;CH,
d
R = C&z.tbd;CSiMe
3
,
e
R = C&z.tbd;CPh,
f
R = C&z.tbd;CC
6
F
4
OMe,
g
R = C&z.tbd;CC
6
H
3
(CF
3
)
2
,
h
R = C
6
F
5
,
i
R = C
6
H
3
(CF
3
)
2
) as mixtures of
E
and
Z
isomers. The dinuclear complexes
5ac
are obtained from the reaction of
1
with the dilithio or dimagnesium compound
4ac
as the
Z
,
Z
-,
E
,
Z
- and
E
,
E
-isomers, respectively. (CO)
5
Cr(CNCF&z.dbd;CFC&z.tbd;CC&z.tbd;CCF&z.dbd;CFNC)Cr(CO)
5
7
is obtained as a mixture of
Z
,
Z
-,
Z
,
E
- and
E
,
E
-isomers from (CO)
5
Cr(CNCF&z.dbd;CFC&z.tbd;CH
3d
by Eglington-Glaser coupling. (CO)
5
Cr(CNCF&z.dbd;CFC&z.tbd;CCF&z.dbd;CFNC)Cr(CO)
5
6
and (CO)
5
Cr(CNCF&z.dbd;CFC&z.tbd;CC&z.tbd;CCF&z.dbd;CFNC)Cr(CO)
5
7
react with octacarbonyldicobalt forming the cluster compounds
Z
,
Z
-[{
2
-
2
-(CO)
5
Cr(CNCF&z.dbd;CFC&z.tbd;CCF&z.dbd;CFNC)Cr(CO)
5
}Co
2
(CO)
6
]
Z
,
Z
-
8
,
E
,
Z
-[{
2
-
2
-(CO)
5
Cr(CNCF&z.dbd;CFC&z.tbd;CCF&z.dbd;CFNC)Cr(CO)
5
}Co
2
(CO)
6
]
E
,
Z
-
8
and
E
,
E
-[{
2
-
2
-(CO)
5
Cr(CNCF&z.dbd;CFC&z.tbd;CCF&z.dbd;CFNC)Cr(CO)
5
}Co
2
(CO)
6
]
E
,
E
-
8
and
Z
,
Z
-[{
2
-
2
-(CO)
5
Cr(CNCF&z.dbd;CFC&z.tbd;CC&z.tbd;CCF&z.dbd;CFNC)Cr(CO)
5
}{Co
2
(CO)
6
}
2
]
Z
,
Z
-
9
,
E
,
Z
-[{
2
-
2
-(CO)
5
Cr(CNCF&z.dbd;CFC&z.tbd;CC&z.tbd;CCF&z.dbd;CFNC)Cr(CO)
5
}{Co
2
(CO)
6
}
2
]
E
,
Z
-
9
and
E
,
E
-[{
2
-
2
-(CO)
5
Cr(CNCF&z.dbd;CFC&z.tbd;CC&z.tbd;CCF&z.dbd;CFNC)Cr(CO)
5
}{Co
2
(CO)
6
}
2
]
Z
,
Z
-
9
, respectively. The crystal and molecular structures of
E
-
3d
,
Z
-
3h
,
Z
,
Z
-
8
,
E
,
Z
-
8
and
Z
,
Z
-
9
were elucidated by single-crystal X-ray crystallography.
The carbon carbon coupling reaction by nucleophilic attack of the trifluoroethenyl isocyanide complex (CO)
5
Cr(CNCF&z.dbd;CF
2
) by lithium or Grignard compounds yields isocyanide complexes as mixtures of
E
and
Z
isomers. |
|---|---|
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c1dt11382h |