Trihydridosilyl-terminated polysilanes and methods of preparation
View Patent ↗Novel trihydridosilyl-terminated polysilanes and methods for their synthesis, which are applicable to other polysilanes, are provided. The synthetic methods provide for facile preparation of products with minimal handling of pyrophoric intermediates and byproducts. The novel compounds contain at least three silicon-silicon bonds and at least one terminal silicon atom having three hydrogen substituents.
1. A trihydridosilyl-terminated polysilane having formula (1), comprising at least four silicon atoms and at least one silicon terminus bonded to three hydrogen atoms,
wherein R represents an organic substituent, R 2 and R 3 are not identical and are independently selected from the group consisting of an organic substituent, a hydrogen, and a substituted silyl group, R 4 , R 5 , and R 6 are independently selected from the group consisting of an organic substituent, a substituted silicon atom and hydrogen, and m and n are each independently integers selected so that the total number of silicon atoms is at least 4.
2. The trihydridosilyl-terminated polysilane according to claim 1 , wherein the number of silicon atoms is not more than about 10.
3. The trihydridosilyl-terminated polysilane according to claim 1 , wherein R 4 , R 5 , and R 6 are hydrogen.
4. The trihydridosilyl-terminated polysilane according to claim 3 , wherein R═R 2 ═CH 3 , n=2, and m=0.
5. The trihydridosilyl-terminated polysilane according to claim 3 , wherein R═R 2 ═CH 3 , n is an integer of about 3 to 8, and m=0.
6. The trihydridosilyl-terminated polysilane according to claim 3 , wherein n=1, m=0, R═SiH 3 , and R 2 =2-ferrocenylethenyl.
7. A method for preparing a trihydridosilyl-terminated polysilane comprising:
(a) preparing a non-pyrophoric aryl-substituted polysilane comprising at least four silicon atoms and an aryl-substituted silicon terminus;
(b) halogenating the aryl-substituted polysilane to produce a halogenated polysilane; and
(c) reducing the halogenated polysilane to yield a trihydridosilyl-terminated polysilane.
8. The method according to claim 7 , wherein the aryl-substituted silicon terminus comprises between one and three aryl substituents.
9. The method according to claim 7 , wherein the aryl substituents are selected from the group consisting of phenyl, tolyl, and anisyl.
10. The method according to claim 7 , further comprising purifying the aryl-substituted polysilane by a method selected from the group consisting of distillation, liquid chromatography, and crystallization.
11. The method according to claim 7 , further comprising purifying the halogenated polysilane by a method selected from the group consisting of distillation, liquid chromatography, and crystallization.
12. The method according to claim 7 , wherein the trihydridosilyl-terminated polysilane comprises not more than about 10 silicon atoms.
13. The method according to claim 7 , wherein the trihydrido-terminated polysilane is a trihydrido-terminated perhydridopolysilane.
14. The method according to claim 7 , wherein the trihydrido-terminated polysilane has formula (1):
wherein R represents an organic substituent, R 2 and R 3 are not identical and are independently selected from the group consisting of an organic substituent, a hydrogen, and a substituted silyl group, R 4 , R 5 , and R 6 are independently selected from the group consisting of an organic substituent, a substituted silicon atom and hydrogen, and m and n are each independently integers selected so that the total number of silicon atoms is at least 4.
15. A method for preparing a trihydridosilyl-terminated oligodimethylsilane comprising:
(a) coupling a halogen-terminated oligosilane with an alkali metal salt of a mono-, di-, or tri-aryl silane to form a coupling product;
(b) halogenating the coupling product to form a halogenated intermediate; and
(c) reducing the halogenated intermediate to form a trihydridosilyl-terminated oligodimethylsilane.
16. The method according to claim 15 , wherein the alkali metal comprises lithium.
17. The method according to claim 15 , wherein the arylsilane is selected from the group consisting of a triarylchlorosilane, a diarylhydrogenchlorosilane, and an aryldihydrogenchlorosilane.
18. The method according to claim 15 , wherein the aryl group is selected from the group consisting of phenyl, tolyl, and anisyl.
19. The method according to claim 15 , wherein step (b) is performed using HCl or HBr in the presence of a Lewis Acid.
20. The method according to claim 15 , wherein the trihydridosilyl-terminated oligodimethylsilane has formula (3), wherein n is an integer greater than 2: