HALOGEN FREE SYNTHESES OF AMINOSILANES BY CATALYTIC DEHYDROGENATIVE COUPLING

摘要

Compounds and method of preparation of Si—X and Ge—X compounds (X═N, P, As and Sb) via dehydrogenative coupling between the corresponding unsubstituted silanes and amines (including ammonia) or phosphines catalyzed by metallic catalysts is described. This new approach is based on the catalytic dehydrogenative coupling of a Si—H and a X—H moiety to form a Si—X containing compound and hydrogen gas (X═N, P, As and Sb). The process can be catalyzed by transition metal heterogenous catalysts such as Ru(0) on carbon, Pd(0) on MgO) as well as transition metal organometallic complexes that act as homogeneous catalysts. The —Si—X products produced by dehydrogenative coupling are inherently halogen free. Said compounds can be useful for the deposition of thin films by chemical vapor deposition or atomic layer deposition of Si-containing films.

主权项

1. A compound having the formula comprising: where n1=1 to (2(k+1)−n2); n2=0 to (2(k+1)−n1); k=2 to 6; R1 and R3 are independently selected from the group consisting of H, linear or branched C1 to C6 alkyl, linear or branched C1 to C8 alkenyl, linear or branched C1 to C8 alkynyl, C6 to C10 aryl, linear or branched C1 to C6 alkyl ether, silyl, trimethyl silyl, or linear or branched C1 to C6 alkyl-substituted silyl; R2 and R4 are independently selected from the group consisting of linear or branched C1 to C6 alkyl, linear or branched C1 to C8 alkenyl, linear or branched C1 to C8 alkynyl, C6 to C10 aryl, linear or branched C1 to C6 alkyl ether, silyl, trimethyl silyl, or linear or branched C1 to C6 alkyl-substituted silyl; E is a group IVb element selected from the group consisting of Si or Ge; the amino groups may be bound to any E atom, the said compounds exclude [(R1R2N)3−xHxSi—Si(NR3R4)3−yHy] wherein R1, R2, R3 and R4 are independently any substituted or unsubstituted linear, branched or cyclic alkyl group, and x,y=0, 1 or 2, (R1R2N)n—SiH(3−n)SiH3 Wherein R1 is selected from a linear or branched C3 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C1 to C6 dialkylamino group, an electron withdrawing group, a C3 to C10 cyclic alkyl group, and a C6 to C10 aryl group; R2 is selected from H, linear or branched C1 to C10 alkyl group, a linear or branched C3 to C6 alkenyl group, a linear or branched C3 to C6 alkynyl group, a C1 to C6 dialkylamino group, a C3 to C10 cyclic alkyl group, a C6 to C10 aryl group, an electron withdrawing group and a C4 to C10 aryl group; n=1 or 2; wherein R1 and R2 are linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring; and wherein, when n=2, and R1 and or R2 or both R1, or both R2 are linked together to form a ring, ((R)HN)3—Si—Si—(NH(R))3 Each R is independently selected from C1 to C4 hydrocarbyl, (Et2N)SiH2—SiH2(NEt2), (Et2N)SiH2—SiH2—SiH2(NEt2), SiH3—SiH(NEt2)—SiH(NEt2)—SiH3, [(CH3)3Si—)2N]—SiH2—SiH2—SiH2—[N(—Si(CH3)3)2], [(CH3)3Si—)2N]—SiH2—SiH2—SiH2—SiH2—[N(—Si(CH3)3)2],and further excluding halogen free H3SiNEt2.