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Park, Joon-Taik 2014-12-15T23:18:08Z 2014-12-15T23:18:08Z 10000-01-01 1983 1983 The present study involves the synthesis, structure, and reactivity of new tungsten-triosmium (WOs(,3)) cluster compounds. The presence of a tungsten atom in the cluster framework imparts a considerably different reactivity pattern than that observed in triosmium chemistry. The reaction of H(,2)Os(,3)(CO)(,10) with CpW(CO)(,2)(CTol){Cp = (eta)('5)-C(,5)H(,5); Tol = p - C(,6)H(,4)CH(,3)} yields three products under mild conditions: CpWOs(,3)(CO)(,11){(mu)(,3)-(eta)('2)-C(O)CH(,2)Tol} (1), Cp(,2)W(,2)Os(CO)(,7)((mu)(,3)-(eta)('2)-C(,2)Tol(,2)) (2), and CpWOs(,3)(CO)(,10)((mu)(,3)-CTol)(,2)H (3). Compound 1 undergoes acyl CO bond scission to provide the doubly-bridging oxo-alkylidyne compound, CpWOs(,3)(CO)(,9)((mu)-O)((mu)(,3)-CCH(,2)Tol) (4). Compound 3 undergoes a degenerate framework rearrangement that interchanges the two inequivalent (mu)(,3)-CTol groups. In addition, the dialkylidyne compound 3 clearly transforms to a symmetrical dialkylidyne complex, CpWOs(,3)(CO)(,9)((mu)(,3)-CTol)(,2)H (5). Compound 4 exhibits reactivity such as oxidative addition of a benzylic hydrogen and conversion to a hydrido-alkylidene compound by dihydrogen, yielding CpWOs(,3)(CO)(,9)((mu)-O)((mu)-CCHTol)H (6) and two isomers of CpWOs(,3)(CO)(,9)((mu)-O)((mu)-CHCH(,2)Tol)H (7), respectively. Reactions of Os(,3)(CO)(,10)(NCMe)(,2) and Os(,3)(CO)(,9)(C(,2)Ph)(,2) with CpW(CO)(,2)(CTol) provides the complexes of CpWOs(,3)(CO)(,11)((mu)(,3)-CTol) (8) and CpWOs(,3)(CO)(,10)-(C(,3)Ph(,2)Tol) (9), respectively.(,) Reactions of CpWOs(,3)(CO)(,12)H with a series of alkynes (RC(TBOND)CR) have resulted in the isolation of two isomeric alkyne derivatives, CpWOs(,3)(CO)(,10)((mu)(,3)-(eta)('2)-C(,2)R(,2))H. Some of these complexes (R = CO(,2)Et, Cf(,3)) undergo irreversible thermal isomerization from one isomer to the other. Diaryl alkyne complexes (R = Ph, Tol) undergo facile intramolecular C(TBOND)C bond scission reactions to yield the corresponding dialkyidyne derivatives, CpWOs(,3)(CO)(,9)((mu)(,3)-CR)(,2)H. Made available in DSpace on 2014-12-15T23:18:08Z (GMT). No. of bitstreams: 1 8410016.pdf: 4566490 bytes, checksum: d152422cea2906d0475cc9124c5bc339 (MD5) Previous issue date: 1983 Embargo set by: Seth Robbins for item 70413 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 173 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1983. http://hdl.handle.net/2142/70247 (UMI)AAI8410016 Chemistry, Inorganic Some Organometallic Chemistry of Tungsten-Triosmium Cluster Compounds text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.