Reactivity of Group 10 halides toward
(Ph2PN![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
)C(Ph)[N(SiMe3)2],
(NC5H4){(Ph2PN)C[N(SiMe
3)2]}-4 and
C6H4{C(NPPh2)[N(SiMe
3)2]}2-1,4
Abstract
Interaction of [NiBr
2
(dme)]
(dme = 1,2-dimethoxyethane) with 1 equivalent of
(Ph
2
PN)C(Ph)[N(SiMe
3
)
2
]
L
1
in tetrahydrofuran gave
cis-[NiBr
2
{(Ph
2
PNH)C(Ph)(
NH)}] 1, metathesis of this compound with excess
NH
4
BF
4
in methanol gave
cis-[Ni{(Ph
2
PNH)C(Ph)(NH)}
2
][BF
4
]
2
2. Reaction of
[NiBr
2
(dme)] with 1 equivalent of
(NC
5
H
4
){Ph
2
PN)C[N(SiMe
3
)
2
]}-4 L
3
followed by metathesis
with excess NH
4
BF
4
in methanol gave
cis-[Ni{(NC
5
H
4
)[(Ph
2
PNH)
C(NH)]-4}
2
][BF
4
]
2
3.
Reaction of [PdCl
2
(PhCN)
2
] with 1 equivalent of
L
1
in acetonitrile gave
cis-[PdCl
2
{(Ph
2
PNH)C(Ph)(
NH)}] 4, and with 0.5 equivalent of
C
6
H
4
{C(NPPh
2
)[N(SiMe
3
)
2
]}
2
-1,4 L
2
in
tetrahydrofuran gave
cis-[(PdCl
2
)
2
{C
6
H
4
[C(NPPh
2
){N(SiMe
3
)
2
}]
2
-1,4}] 5 and
cis-[(PdCl
2
)
2
{C
6
H
4
[C(NHPPh
2
)(NH)]
2
-1,4}] 6.
Interaction of [PdCl
2
(PhCN)
2
] with L
3
in 1∶1 and 3∶2 molar ratios gave
cis-[PdCl
2
{(NC
5
H
4
)[(Ph
2
PNH)C(NH)]-4}] 7 and
trans-[PdCl
2
{cis-PdCl
2
[
(NC
5
H
4
){(Ph
2
PNH)C(NH)
}-4]}
2
] 8, respectively. Reaction of
[MCl
2
(PhCN)
2
] (M = Pd or Pt) with 2
equivalents of L
3
followed by metathesis with excess
NH
4
BF
4
in methanol gave
cis-[M{(NC
5
H
4
)[(Ph
2
PNH)
C(NH)]-4}{(NC
5
H
4
)[(Ph
2
PNH)C(N)]-4}][BF
4
] (Pd 9 or Pt 10).
Crystal structures of compounds 1, 4, 7, 8, 9 and 10 have been
determined.
)C(Ph)[N(SiMe
3
)
2
]
L
1
in tetrahydrofuran gave
cis-[NiBr
2
{(Ph
2
PNH)C(Ph)(
NH)}] 1, metathesis of this compound with excess
NH
4
BF
4
in methanol gave
cis-[Ni{(Ph
2
PNH)C(Ph)(NH)}
2
][BF
4
]
2
2. Reaction of
[NiBr
2
(dme)] with 1 equivalent of
(NC
5
H
4
){Ph
2
PN)C[N(SiMe
3
)
2
]}-4 L
3
followed by metathesis
with excess NH
4
BF
4
in methanol gave
cis-[Ni{(NC
5
H
4
)[(Ph
2
PNH)
C(NH)]-4}
2
][BF
4
]
2
3.
Reaction of [PdCl
2
(PhCN)
2
] with 1 equivalent of
L
1
in acetonitrile gave
cis-[PdCl
2
{(Ph
2
PNH)C(Ph)(
NH)}] 4, and with 0.5 equivalent of
C
6
H
4
{C(NPPh
2
)[N(SiMe
3
)
2
]}
2
-1,4 L
2
in
tetrahydrofuran gave
cis-[(PdCl
2
)
2
{C
6
H
4
[C(NPPh
2
){N(SiMe
3
)
2
}]
2
-1,4}] 5 and
cis-[(PdCl
2
)
2
{C
6
H
4
[C(NHPPh
2
)(NH)]
2
-1,4}] 6.
Interaction of [PdCl
2
(PhCN)
2
] with L
3
in 1∶1 and 3∶2 molar ratios gave
cis-[PdCl
2
{(NC
5
H
4
)[(Ph
2
PNH)C(NH)]-4}] 7 and
trans-[PdCl
2
{cis-PdCl
2
[
(NC
5
H
4
){(Ph
2
PNH)C(NH)
}-4]}
2
] 8, respectively. Reaction of
[MCl
2
(PhCN)
2
] (M = Pd or Pt) with 2
equivalents of L
3
followed by metathesis with excess
NH
4
BF
4
in methanol gave
cis-[M{(NC
5
H
4
)[(Ph
2
PNH)
C(NH)]-4}{(NC
5
H
4
)[(Ph
2
PNH)C(N)]-4}][BF
4
] (Pd 9 or Pt 10).
Crystal structures of compounds 1, 4, 7, 8, 9 and 10 have been
determined.
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![[double bond, length as m-dash]](https://www.rsc.org/images/entities/h2_char_e001.gif)
)C(Ph)[N(SiMe3)2],
(NC5H4){(Ph2PN