Reactivity of R2AlH (R = Me, Bui) and Me3M (M = Al, Ga, In) toward the Silylphosphines P(SiMe3)3 and HP(SiMe3)2
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- 作者：Larry K. Krannich ; Charles L. Watkins ; Steven J. Schauer ; and Charles H. Lake
- 刊名：Organometallics
- 出版年：1996
- 出版时间：September 17, 1996
- 年：1996
- 卷：15
- 期：19
- 页码：3980 - 3984
- 全文大小：155K
- 年卷期：v.15,no.19(September 17, 1996)
- ISSN：1520-6041
文摘
The reactivities of Me2AlH withP(SiMe3)3 and of Me3M (M = Al,Ga, In) and Bui2AlHwith P(SiMe3)3 andHP(SiMe3)2 were monitored withmultinuclear NMR to determine thetrend for adduct formation and establish the role that the Me andBui moieties and M playin influencing the nature of the possible 1,2-elimination product.1:1 adducts were obtainedin the Me3M/P(SiMe3)3 systems withno tendency toward room-temperature, 1,2-eliminationreactivity. Thermolysis at 100 
C gave the following order ofreactivity for SiMe4elimination:Me3In·P(SiMe3)3 >Me3Ga·P(SiMe3)3 >>Me3Al·P(SiMe3)3.With the Me3M/HP(SiMe3)2 systems, only Me3Algave an isolable adduct, which eliminated CH4 uponheatingto form[Me2AlP(SiMe3)2]2.Although NMR spectral data indicated adduct formation intheMe3Ga and Me3In systems, theseunderwent CH4 elimination to yield the respective[Me2MP(SiMe3)2]2 species. Thevariable-temperature, multinuclear NMR study of theMe2AlH/P(SiMe3)3 system indicated adduct formation at-90 C and subsequent conversion to cyclicoligomeric[Me2AlP(SiMe3)2]n[Me2AlH]mspecies at -80 C that ultimately produced[Me2AlP(SiMe3)2]2. Thereactivity of Bui2AlH towardP(SiMe3)3 andHP(SiMe3)2 is much slowerthen that of Me2AlH. In theBui2AlH/HP(SiMe3)2system, H2 elimination is favored and[Bui2AlP(SiMe3)2]2 andBui2AlP(SiMe2)2·Bui2AlP(H)SiMe3are formed. An X-ray structure analysisof[Bui2AlP(SiMe3)2]2establishes the planarity of the (AlP)2 core.
C gave the following order ofreactivity for SiMe4elimination:Me3In·P(SiMe3)3 >Me3Ga·P(SiMe3)3 >>Me3Al·P(SiMe3)3.With the Me3M/HP(SiMe3)2 systems, only Me3Algave an isolable adduct, which eliminated CH4 uponheatingto form[Me2AlP(SiMe3)2]2.Although NMR spectral data indicated adduct formation intheMe3Ga and Me3In systems, theseunderwent CH4 elimination to yield the respective[Me2MP(SiMe3)2]2 species. Thevariable-temperature, multinuclear NMR study of theMe2AlH/P(SiMe3)3 system indicated adduct formation at-90 C and subsequent conversion to cyclicoligomeric[Me2AlP(SiMe3)2]n[Me2AlH]mspecies at -80 C that ultimately produced[Me2AlP(SiMe3)2]2. Thereactivity of Bui2AlH towardP(SiMe3)3 andHP(SiMe3)2 is much slowerthen that of Me2AlH. In theBui2AlH/HP(SiMe3)2system, H2 elimination is favored and[Bui2AlP(SiMe3)2]2 andBui2AlP(SiMe2)2·Bui2AlP(H)SiMe3are formed. An X-ray structure analysisof[Bui2AlP(SiMe3)2]2establishes the planarity of the (AlP)2 core.