Reactivity of R2AlH (R = Me, Bui) and Me3M (M = Al, Ga, In) toward the silylphosphines P(SiMe3)3 and HP(SiMe3)2

Academic Article

Abstract

  • The reactivities of Me AlH with P(SiMe ) and of Me M (M = Al, Ga, In) and Bu AlH with P(SiMe ) and HP(SiMe ) were monitored with multinuclear NMR to determine the trend for adduct formation and establish the role that the Me and Bu moieties and M play in influencing the nature of the possible 1,2-elimination product. 1:1 adducts were obtained in the Me M/P(SiMe ) systems with no tendency toward room-temperature, 1,2-elimination reactivity. Thermolysis at 100 °C gave the following order of reactivity for SiMe elimination: Me In·P(SiMe ) > Me Ga·P(SiMe ) > > Me Al·P(SiMe ) . With the Me M/ HP(SiMe ) systems, only Me Al gave an isolable adduct, which eliminated CH upon heating to form [Me AlP(SiMe ) ] . Although NMR spectral data indicated adduct formation in the Me Ga and Me In systems, these underwent CH elimination to yield the respective [Me -MP(SiMe ) ] species. The variable-temperature, multinuclear NMR study of the Me AlH/ P(SiMe ] system indicated adduct formation at -90 °C and subsequent conversion to cyclic oligomeric [Me AlP(SiMe ] ] [Me AlH] species at -80 °C that ultimately produced [Me -AlP(SiMe ) ] . The reactivity of Bu AlH toward P(SiMe ) and HP(SiMe ) is much slower then that of Me AlH. In the Bu AlH/HP(SiMe ) system, H elimination is favored and [Bu -AlP(SiMe ) ] and Bu AlP(SiMe ) ·Bu AlP(H)SiMe are formed. An X-ray structure analysis of [Bu AlP(SiMe ) ] establishes the planarity of the (AlP) core. 2 3 3 3 2 3 3 3 2 3 3 3 4 3 3 3 3 3 3 3 3 3 3 3 2 3 4 2 3 2 2 3 3 4 2 3 2 2 2 3 3 2 3 2 n 2 m 2 3 2 2 2 3 3 3 2 2 2 3 2 2 i2 3 2 2 i2 2 2 2 3 2 3 2 2 2 i i i i i i
  • Published In

  • Organometallics  Journal
  • Digital Object Identifier (doi)

    Author List

  • Krannich LK; Watkins CL; Schauer SJ; Lake CH
  • Start Page

  • 3980
  • End Page

  • 3984
  • Volume

  • 15
  • Issue

  • 19