om9604177_si_001.pdf (216.05 kB)
Reactivity of R2AlH (R = Me, Bui) and Me3M (M = Al, Ga, In) toward the Silylphosphines P(SiMe3)3 and HP(SiMe3)2
journal contribution
posted on 1996-09-17, 00:00 authored by Larry K. Krannich, Charles L. Watkins, Steven J. Schauer, Charles H. LakeThe reactivities of Me2AlH with
P(SiMe3)3 and of Me3M (M = Al,
Ga, In) and Bui2AlH
with P(SiMe3)3 and
HP(SiMe3)2 were monitored with
multinuclear NMR to determine the
trend for adduct formation and establish the role that the Me and
Bui moieties and M play
in influencing the nature of the possible 1,2-elimination product.
1:1 adducts were obtained
in the Me3M/P(SiMe3)3 systems with
no tendency toward room-temperature, 1,2-elimination
reactivity. Thermolysis at 100 °C gave the following order of
reactivity for SiMe4
elimination:
Me3In·P(SiMe3)3 >
Me3Ga·P(SiMe3)3 >>
Me3Al·P(SiMe3)3.
With the Me3M/HP(SiMe3)2 systems, only Me3Al
gave an isolable adduct, which eliminated CH4 upon
heating
to form
[Me2AlP(SiMe3)2]2.
Although NMR spectral data indicated adduct formation in
the
Me3Ga and Me3In systems, these
underwent CH4 elimination to yield the respective
[Me2MP(SiMe3)2]2 species. The
variable-temperature, multinuclear NMR study of the
Me2AlH/P(SiMe3)3 system indicated adduct formation at
−90 °C and subsequent conversion to cyclic
oligomeric
[Me2AlP(SiMe3)2]n[Me2AlH]m
species at −80 °C that ultimately produced
[Me2AlP(SiMe3)2]2. The
reactivity of Bui2AlH toward
P(SiMe3)3 and
HP(SiMe3)2 is much slower
then that of Me2AlH. In the
Bui2AlH/HP(SiMe3)2
system, H2 elimination is favored and
[Bui2AlP(SiMe3)2]2 and
Bui2AlP(SiMe2)2·Bui2AlP(H)SiMe3
are formed. An X-ray structure analysis
of
[Bui2AlP(SiMe3)2]2
establishes the planarity of the (AlP)2 core.
History
Usage metrics
Categories
- Space Science
- Physical Sciences not elsewhere classified
- Medicine
- Genetics
- Molecular Biology
- Chemical Sciences not elsewhere classified
- Immunology
- Biological Sciences not elsewhere classified
- Information Systems not elsewhere classified
- Mathematical Sciences not elsewhere classified
- Developmental Biology
- Computational Biology
Keywords
Licence
Exports
RefWorks
BibTeX
Ref. manager
Endnote
DataCite
NLM
DC