Reactions of α-lithiated phosphinimines with PhCN; the
crystal structure of
[![[upper bond 1 start]](https://www.rsc.org/images/entities/char_e010.gif)
K{N(H)C(Ph)C(H)P(Ph)2![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
N![[upper bond 1 end]](https://www.rsc.org/images/entities/char_e011.gif)
SiMe
3}(tmen)]2 (tmen =
Me2NCH2CH2NMe2)
Abstract
Treatment of the α-lithiated phosphinimine
Li{CH(R′)P(R)
2
NSiMe
3
} with benzonitrile yielded (via a trimethylsilyl
or hydrogen 1,3 C → N shift) the
trimethylsilyliminophosphoranylenamidolithium complex
Li{N(R′)C(Ph)C(H)P(R)
2
N
SiMe
3
} (R = Me,
R′ = SiMe
3
1; R = Ph,
R′ = SiMe
3
2; or R = Ph,
R′ = H 3). Complex 2 was transformed into the
corresponding potassium complex 4 by an exchange reaction with
KOBu
t
. Crystallisation of 4 from hexane in the presence of
Me
2
NCH
2
CH
2
NMe
2
(tmen) gave
the tmen adduct 5 and a trace of the partially hydrolysed product
[K{N(H)C(Ph)C(H)P(Ph)
2
NSiMe
3
}(tmen)]
2
6, which was characterised by a
single crystal X-ray diffraction study as a dinuclear complex with each
of the two potassium atoms in a different co-ordination environment.
Complex 1 or 2 was hydrolysed to form the neutral
iminophosphoranylenamine
N(SiMe
3
)C(Ph)C(H)P(R)
2
N(SiMe
3
)
H 7 or 8, which showed (
1
H NMR spectroscopy) the
presence of hydrogen bonds.
Li{CH(R′)P(R)
2
NSiMe
3
} with benzonitrile yielded (via a trimethylsilyl
or hydrogen 1,3 C → N shift) the
trimethylsilyliminophosphoranylenamidolithium complex
Li{N(R′)C(Ph)C(H)P(R)
2
N
SiMe
3
} (R = Me,
R′ = SiMe
3
1; R = Ph,
R′ = SiMe
3
2; or R = Ph,
R′ = H 3). Complex 2 was transformed into the
corresponding potassium complex 4 by an exchange reaction with
KOBu
t
. Crystallisation of 4 from hexane in the presence of
Me
2
NCH
2
CH
2
NMe
2
(tmen) gave
the tmen adduct 5 and a trace of the partially hydrolysed product
[K{N(H)C(Ph)C(H)P(Ph)
2
NSiMe
3
}(tmen)]
2
6, which was characterised by a
single crystal X-ray diffraction study as a dinuclear complex with each
of the two potassium atoms in a different co-ordination environment.
Complex 1 or 2 was hydrolysed to form the neutral
iminophosphoranylenamine
N(SiMe
3
)C(Ph)C(H)P(R)
2
N(SiMe
3
)
H 7 or 8, which showed (
1
H NMR spectroscopy) the
presence of hydrogen bonds.
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![[upper bond 1 start]](https://www.rsc.org/images/entities/h2_char_e010.gif)
K{N(H)C(Ph)C(H)P(Ph)2![[double bond, length as m-dash]](https://www.rsc.org/images/entities/h2_char_e001.gif)
N![[upper bond 1 end]](https://www.rsc.org/images/entities/h2_char_e011.gif)
SiMe
3}(tmen)]2 (tmen =
Me2NCH2CH2NMe2)