Metal-Siloxy Condensation Reactions
Abstract
In search for a prototype inorganic condensation reaction that could be used later for study of inorganic polycondensation reactions, it was found that the reaction of NaOSiPhi3 with Phi3SnCl, (n-C4H9)2SnCl2, and (CH3)2SnCl2 in an aprotic solvent is consistent with the overall equations: Phi3SnCl + NaOSiPhi3 + Phi3SiOSnPhi3 + NaCl (n-C4H9)3SnCl2 + 2NaOSiChi3 + (n-C4H9)2Sn(OSiPhi3)2 + 2NaCl (CH3)2SnCl2 +2NaOSiPhi32 + 2Nacl with no evidence that significant side reactions occur. These reactions appear to go to completion as shown by quantitative determination of NaCl and the stannosiloxane product. The sodium chloride by-product forms immediately, indicating that these reactions at room temperature in benzene are extremely rapid. Quantitative rate measurements could not be made but the stoichiometry of the reaction was established. In the course of the study, several new stannosiloxanes were prepared and characterized by infrared spectroscopy and elemental analysis. The preparation, characterization, and some properties are reported for siloxy derivatives of bis( cyclopentadienyl)titanium(IV). Monosiloxy derivatives were prepared by the reaction of the appropriate sodium silanolate with bis(cyclopentadienyl) titanium dichloride in toluene at 75-90C under anhydrous conditions. The compounds prepared and characterized were trimethylsiloybis(cyclopentadienyl)titanium chloride, methyldiphenylsiloybis(cyclopentadienyl)titanium chloride, and triphenylsiloxybis(cyclopentadienyl)titanium chloride. These Ti-O-Si compounds are orange crystalline substances; the triphenylsiloxy derivative melts at 201-204 C. Replacement of C6H5 by CH3 groups markedly lowers the melting points and thermal stabilities. Bis(triphenylsiloxy)bis(cyclopentadienyl)titanium was prepared in toluene at 75-90 C from bis(cyclopentadienyl)titanium dihalide and sodium triphenylsilanolate or triphenylsilanol.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 1962
- Accession Number
- ADA470515
Entities
People
- Jack B. Kinsinger
- Robert N. Hammer
Organizations
- Michigan State University