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Cyanide-alkene competition in a diiron complex and isolation of a multisite (cyano)alkylidene-alkene species
The μ-(amino)alkylidyne complex [Fe 2 Cp 2 (CO) 2 (μ-CO){μ-CNMe(CH 2 CH&z.dbd;CH 2 )}]CF 3 SO 3 , [ 1 ]CF 3 SO 3 , reacted with NBu 4 CN in dichloromethane affording the μ-(cyano)(amino)alkylidene [Fe 2 Cp 2 (CO) 2 (μ-CO){μ-C(CN)N(Me)(CH 2 CH&z.dbd;CH 2 )}], 2 , in 91% yield. Decarbonylation...
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| Published in: | Dalton transactions : an international journal of inorganic chemistry 2022-02, Vol.51 (5), p.1936-1945 |
|---|---|
| Main Authors: | , , , , , , |
| Format: | Article |
| Language: | English |
| Subjects: | |
| Citations: | Items that this one cites Items that cite this one |
| Online Access: | Get full text |
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| Summary: | The μ-(amino)alkylidyne complex [Fe
2
Cp
2
(CO)
2
(μ-CO){μ-CNMe(CH
2
CH&z.dbd;CH
2
)}]CF
3
SO
3
, [
1
]CF
3
SO
3
, reacted with NBu
4
CN in dichloromethane affording the μ-(cyano)(amino)alkylidene [Fe
2
Cp
2
(CO)
2
(μ-CO){μ-C(CN)N(Me)(CH
2
CH&z.dbd;CH
2
)}],
2
, in 91% yield. Decarbonylation of
2
by using Me
3
NO in acetone at room temperature yielded [Fe
2
Cp
2
(CO)(μ-CO){μ-κ
3
C
-C(CN)N(Me)(CH
2
CH&z.dbd;CH
2
)}],
3
, containing a multidentate alkylidene−alkene ligand occupying both a bridging site and a terminal site, in admixture with the μ-(amino)alkylidyne cyanide product [Fe
2
Cp
2
(CN)(CO)(μ-CO){μ-CN(Me)(CH
2
CH&z.dbd;CH
2
)}],
4
. The reaction of the μ-(amino)alkylidyne imine complex [Fe
2
Cp
2
(CO)(μ-CO)(NH&z.dbd;CPh
2
){μ-CN(Me)(CH
2
CH&z.dbd;CH
2
)}]CF
3
SO
3
, [
7
]CF
3
SO
3
, with NBu
4
CN gave
3
with an optimized yield of 75%
via
imine elimination. According to DFT calculations,
3
is less stable than its geometric isomer
4
by 13.4 kcal mol
−1
and quantitative conversion to
4
was achieved by refluxing a THF solution of
3
for 2 hours. No replacement of alkene coordination occurred upon treating
3
with CO or PPh
3
. The previously unknown compounds
2
,
3
,
4
and [
7
]CF
3
SO
3
were fully characterized by analytical and spectroscopic techniques and the structure of
3
was elucidated by single crystal X-ray diffraction.
A cyanide addition/decarbonylation sequence in a diiron (allyl)amino-alkylidyne complex results in the formation of an unusual alkylidene-alkenyl species as an isolable intermediate along the route leading to stable metal coordination of the cyanide. |
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| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/d1dt03781a |