A comparative study on the structural and chemical properties of group 13-15 element addition compounds tBu_2PH-EX_3 (E = B, Al, Ga, In; X = Cl, Br)

摘要

The group 13-15 element addition compounds tBu_2PH.EX_3 (E = B, Al, Ga, In; X = Cl, Br) are accessible from the reaction of tBu _2PH with the triel halides EX_3 (E = B, Al, Ga, In; X = Cl, Br) at room temperature. The crystal structures of the group 13-15 element addition compounds iBu_2PHBBr_3 (monoclinic, P ~2_1Jc) and iBu_2PHEBr_3 (E = B, Al, Ga, In) (monoclinic, P~2_1Jc)) are described. When the addition compound iBu_2PH.BBr_3 was treated with one equivalent of LiN(SiMe_3)_2, the reaction led to the formation of the cyclophosphinoborane (tBu_2PBBr_2)_2. The structure of (tBu_2PBBr_2)_2 (monoclinic, C2/m) displays a four-membered P_2B_2 ring whereas the cyclophosphinoalane (Ph_2PAlMe_2)_3 which was obtained from Ph_2PH and AlMe_3 has a six-membered P _3Al_3 ring structure (monoclinic, P~2_1 c). In addition, we report the result of the X-ray structure analysis of the oxidation product of iBu_2PH.BBr_3, the phosphane oxide adduct iBu_2PHO.GaBr_3 (orthorhombic, Pnma) and of the phosphonium salt [iBu_2PH_2]~-[GaBr _4]~- (monoclinic, P_21_n).