טכניון מכון טכנולוגי לישראל
הטכניון מכון טכנולוגי לישראל - בית הספר ללימודי מוסמכים  
Ph.D Thesis
Ph.D StudentMinkovich Boris
SubjectTowards Multiply-Bonded Silicon-Group 15 Elements
Compounds
DepartmentDepartment of Chemistry
Supervisors ? 18? Yitzhak Apeloig
Dr. Dmitry Bravo-Zhivotovs


Abstract

This research main goals are the synthesis, characterization and reactions of new unsaturated Si compounds with a double bond to E (R2Si=EH), where E is a group 15 element, N or P.

            A series of P-protected phosphasilenes (R3Si)2Si=P-ER’3, (R’3E = Me3Sn, nBu3Sn, Me2tBuSi) were synthesized and characterized by multinuclear NMR spectroscopy.

            Reduction of P-protected phosphasilenes (R3Si)2Si=P-ER’3 produces quantitatively corresponding persistent anion-radicals, characterized by EPR spectroscopy, while further reduction towards P-deprotection failed due to Si-P bond fragmentation.

A series of unique η2-π-complexes of a phosphasilene with a transition metals, η2-L2(T.M.)-(R2Si=PH), T.M.= Pt, Pd, Ni were synthesized via LiF or “H2” elimination from corresponding precursors in presence of L4(T.M.)-complexes. η2-L2(T.M.)-(R2Si=PH) complexes were characterized by multinuclear NMR spectroscopy and X-ray crystallography.

            η2-L2Pt-(R2Si=PH) complex has, at least, two additional reactive sites - the P-H bond and the phosphorus lone pair, which can be functionalized.

            η2-L2Pt-(R2Si=PH) was metalated with Li-, Zn-, Hg-, Ag- and Sn-amides, providing unique heterobimetallic complexes respectively, which were characterized by NMR and X-ray.

We demonstrated that the very reactive (R3Si)2Si=PH, although it was not isolated, is a variable bridging ligand for a new type of heterobimetallic complexes.

In parallel, intensive work was done on analogous systems towards functionalized unsaturated R2Si=N-H compounds.