The promotion of air oxidation and carbonyl substitution reactions of [(η5-C5H5)2Mo 2(CO)4(µ-RCCR′)] by trimethylamine N-oxide or nitrosonium tetrafluoroborate: the synthesis of [(η5-C5H5)2Mo 2(O)2(µ-O)(µ-RCCR′)] (R = R′ = CO2Me or Ph; R = H, R′ = Ph; or R = H, R′ = CO2Me) and [(η5-C5H5)2Mo 2(CO)3(NO)(µ-RCCR′)][BF4 ] (R = R′ = CO2 Me, Me or H; or R = H, R′ = CO2Me)
Abstract
Trimethylamine N-oxide promotes the air oxidation of
[(η
5
-C
5
H
5
)
2
Mo
2
(CO)
4
(µ-RCCR′)] to afford the novel
organometallic oxo complexes
[(η
5
-C
5
H
5
)
2
Mo
2
(O)
2
(µ-O)(µ-RCCR′)]
[R = R′ = CO
2
Me or Ph;
R = H, R′ = Ph; or
R = H, R′ = CO
2
Me).
Trimethylamine N-oxide also promotes the near quantitative
substitution of one of the carbonyl groups in
[(η
5
-C
5
H
5
)
2
Mo
2
(CO)
4
(µ-MeO
2
CC
2
CO
2
Me)] by either Bu
t
NC or (MeO)
3
P (L), giving
[(η
5
-C
5
H
5
)
2
Mo
2
(CO)
3
(L)(µ-MeO
2
CC
2
CO
2
Me)] at room temperature. The addition of [NO][BF
4
], in
place of Me
3
NO, to solutions of
[(η
5
-C
5
H
5
)
2
Mo
2
(CO)
4
(µ-RCCR′)] under the same reaction
conditions, does not promote air oxidation but leads instead to the new
dimolybdenum nitrosyl complexes
[(η
5
-C
5
H
5
)
2
Mo
2
(CO)
3
(NO)(µ-RCCR′)][BF
4
]
(R = R′ = CO
2
Me, Me or H; or
R = H, R′ = CO
2
Me). The
structure of
[(η
5
-C
5
H
5
)
2
Mo
2
(CO)
3
(NO)(µ-MeO
2
CC
2
CO
2
Me)][BF
4
] has been determined by X-ray
crystallography.
Please wait while we load your content...
