New ansa-2,2-bis(η-cyclopentadienyl)propane
molybdenum and tungsten compounds and intramolecular
hydrogen–deuterium exchange in methyl-hydride and ethyl-hydride
derivatives
Abstract
The new compounds
[Mo
2
Cl
4
(OEt)
4
(EtOH)
2
],
[Mo{(η-C
5
H
4
)C(C
5
H
10
)(η-C
5
H
4
)}Cl
2
],
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)Cl
2
][BF
4
],
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}(SPh)
2
],*
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}(SPr
i
)
2
],
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}(SPr
i
)(NCMe)][BF
4
],
[M{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}(NCMe)Cl][PF
6
]
(M = Mo or W),*
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}(PPh
3
)Cl][PF
6
],
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}(CNC
6
H
3
Me
2
-
2,6)Cl][PF
6
],*
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}(η
2
-C
2
H
4
)H][B(C
6
F
5
)
4
],*
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}Et(NCMe)][B(C
6
F
5
)
4
],
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}Et(Cl)],*
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}Et(Cl)][BF
4
],
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}H
3
][PF
6
],*
[M{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}Et
2
] (M = Mo or W),*
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}Et(I)],
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}Et(O
2
CPh)],
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}Et(X)] (X = H or D),
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}(CD
3
)
2
],
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}(CD
3
)I],*
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}(CD
3
)H] and
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}Me(D)] have been prepared. The asterisk
indicates the crystal structure has been determined. Evidence is
presented for intramolecular hydrogen–deuterium scrambling
processes in the methyl- and ethyl-hydride compounds. Preliminary
variable-temperature
1
H NMR studies on
[W{(η-C
5
H
4
)CMe
2
(η-C
5
H
4
)}H
A
(H
B
)
2
]
[PF
6
] give a value for J(AB) of 16 000 Hz at
-70 °C.
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