Reactivity of [M(CO)4(nbd)] (M = Cr or Mo; nbd = norbornadiene) toward (Ph2PN)C(Ph)[N(SiMe3)2] and C6H4{C[N(SiMe3)2 ](NPPh2)}2-1,4
Abstract
The interaction of
(Ph
2
PN)C(Ph)[N(SiMe
3
)
2
] with 1
equivalent of [M(CO)
4
(nbd)] (M = Cr or Mo,
nbd = norbornadiene) in diethyl ether gave
cis-[M(CO)
4
{(Me
3
SiN)C(Ph)(NHPPh
2
}] (M = Cr 1 or Mo 2)
in good yield. The interaction of
C
6
H
4
{C(NPPh
2
)[N(SiMe
3
)
2
]}
2
-1,4 with 2 equivalents of
[M(CO)
4
(nbd)] (M = Cr or Mo) in tetrahydrofuran
gave the symmetric dimer
cis-[{M(CO)
4
}{(Ph
2
PNH)(Me
3
SiN)CC
6
H
4
C(NSiMe
3
)(NHPPh
2
)}] (M = Cr 3 or Mo
4) in moderate yield. However, in diethyl ether, this reaction
(M = Mo) gave the unsymmetric
cis-[(OC)
4
Mo{(Ph
2
PNH)(Me
3
SiN)CC
6
H
4
C[N(SiMe
3
)
2
](NPPh
2
)}Mo(CO)
5
] 5 in moderate
yield. Compounds 1–5 have been fully
characterized by analytical and spectroscopic methods and the structures
of 3 and 5 have been established by X-ray
crystallography. A 1,3-silyl shift mechanism has been proposed for the
formation of the products. The NH proton of the bidentate iminophosphine
ligand undergoes facile deuterium exchange with D
2
O at
ambient temperature.
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