Sterically Tuned P ‐Phosphanylamino Phosphaalkenes (Me 3 Si) 2 C=PN( R )PPh 2 and ( i PrMe 2 Si) 2 C=PN( R )PPh 2
Deprotonation of the aminophosphanes Ph 2 PN(H) R 1a – 1h [ R = t Bu ( 1a ), 1‐adamantyl ( 1b ), i Pr ( 1c ), CPh 3 ( 1d ), Ph ( 1e ), 2,4,6‐Me 3 C 6 H 2 (Mes) ( 1f ), 2,4,6‐ t Bu 3 C 6 H 2 (Mes*) ( 1g ), 2,6‐ i Pr 2 C 6 H 3 (DIPP) ( 1h )], followed by reactions of the phosphanylamide salts Li[Ph 2...
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Veröffentlicht in: | Zeitschrift für anorganische und allgemeine Chemie (1950) 2018-04, Vol.644 (7), p.381-390 |
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Sprache: | eng |
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Zusammenfassung: | Deprotonation of the aminophosphanes Ph
2
PN(H)
R
1a
–
1h
[
R
=
t
Bu (
1a
), 1‐adamantyl (
1b
),
i
Pr (
1c
), CPh
3
(
1d
), Ph (
1e
), 2,4,6‐Me
3
C
6
H
2
(Mes) (
1f
), 2,4,6‐
t
Bu
3
C
6
H
2
(Mes*) (
1g
), 2,6‐
i
Pr
2
C
6
H
3
(DIPP) (
1h
)], followed by reactions of the phosphanylamide salts Li[Ph
2
PN
R
]
2a
,
2b
,
2g
, and
2h
with the
P
‐chlorophosphaalkene (Me
3
Si)
2
C=PCl, and of
2a
–
2g
with (
i
PrMe
2
Si)
2
C=PCl, gave the isolable
P
‐phosphanylamino phosphaalkenes (Me
3
Si)
2
C=PN(
R
)PPh
2
3a
,
3b
,
3g
, and (
i
PrMe
2
Si)
2
C=PN(
R
)PPh
2
4a
–
4g
.
31
P NMR spectra, supported by X‐ray structure determinations, reveal that in compounds
2a
,
2b
,
3a
, and
3b
, with bulky N‐alkyl groups the Si
2
C=P–N–P skeleton is non‐planar (orthogonal conformation), whereas
3g
,
3h
, and
4g
with bulky N‐aryl groups exhibit planar conformations of the Si
2
C=P–N–P skeleton. Solid
3g
and
4g
exhibit
cisoid
orientation of the planar C=P–N–C units (planar I) but in solid
3h
the
transoid
rotamer is present (planar II). From
3g
,
4d
, and
4g
mixtures of rotamers were detected in solution by pairs of
31
P NMR patterns (
3h
: line broadening). |
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ISSN: | 0044-2313 1521-3749 |
DOI: | 10.1002/zaac.201700446 |