Hydrozirconation and subsequent phosphination have been developed into a versatile synthetic
methodology leading to formation of phosphorus-carbon bonds. A family of phosphinoalkylsilane
ligand precursors SiHMen(CH₂CH₂CH₂PPh₂)₃₋n (ChelH, I: n = 2; biPSiH, II: n = 1; triPSiH, III: n = 0)
previously prepared via a photo-chemical route were synthesized in this way and the
phosphination step has been shown to be dependent on steric factors. Similar methods have been
used to obtain a group of new ligand precursors, the poly(silaalkyl)phosphines PPhn(CH₂CH₂CH₂PR₂)₃₋n
(12: n = 1; 13: n = 0), which have been isolated and fully characterized. Analogues PPhn(o-C₆H₄SiMe₂H)₃₋n (21 : n = 1; 22: n = 0) containing more rigid benzylic backbones have been prepared
from the corresponding (o-tolyl)phosphines via polylithiation and shown to exhibit temperature
dependent NMR behavior. Poly(silaalkyl)phosphine coordination chemistry has been explored,
yielding an unprecedented trans-bis(silyl) Pt(II) complex Pt[PhP(o-C₆H₄CH₂SiMe₂)₂]PPh₃ (25 ) which
was isolated and characterized by using spectroscopic methods.
The chemistry of [bis(diphenylphosphinopropyl)silyl] hydrido dicarbonyl ruthenium(II), RuH
(biPSi)(CO)₂ (26), has been investigated in detail. The two diastereomers, syn and anti, were
observed to exchange slowly with the two CO groups also scrambling at a comparable rate. A
kinetic study of these two intramolecular isomerization processes suggests the involvement of
dissociation and re-association of the chelate (biPSi) phosphines. Oxygen atom insertion into
the Ru-Si bond of 26 occurs both in a hydrolysis process and direct oxidation by dioxygen. A
labeling experiment suggests the former may involve a molecular dihydrogen intermediate, while
the latter leads to insertion of oxygen atoms into both Ru-Si and Si-C bonds. Chlorination of 26
and subsequent thermal loss of a CO group afforded a novel l6e five coordinate Ru(II) species
RuCl(biPSi)(CO) (42). Reaction of 42 with NaBH₄ or LiAlH₄ gave a mononuclear borohydride complex
Ru(biPSi)(CO)(μ-η²-H₂BH₂) (43) or a rare hydrido anionic complex [fac-Ru(H)₂biPSi)(CO)]⁻ (44),
both of which are extremely sensitive and have been identified in situ by using solution NMR
spectroscopy. The silyl group in 26 was found to exert a stronger trans effect than hydride. / Graduate
| Identifer | oai:union.ndltd.org:uvic.ca/oai:dspace.library.uvic.ca:1828/8451 |
| Date | 23 August 2017 |
| Creators | Zhou, Xiaobing |
| Contributors | Stobart, Stephen R. |
| Source Sets | University of Victoria |
| Language | English, English |
| Detected Language | English |
| Type | Thesis |
| Format | application/pdf |
| Rights | Available to the World Wide Web |
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