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Title Low valent group IV naphthalene and carbonyl chemistry. Part One. Synthesis, characterization and reactivity of low valent titanium naphthalene and carbonyl compounds. Part Two. Synthesis, characterization and reactivity of low valent zirconium and hafnium naphthalene and carbonyl compounds. Part Three. The chemistry of zerovalent titanium alkoxycarbonyl compounds
Creator/Author Yuen, Pong Kau.
Publication Date1993 Jan 01
OSTI IdentifierOSTI ID: 7288352
Resource TypeMiscellaneous
Resource RelationThesis (Ph.D.)
Research OrgMinnesota Univ., Minneapolis, MN (United States)
Subject400201 -- Chemical & Physicochemical Properties; CARBONYLS-- CHEMICAL PREPARATION;HAFNIUM COMPLEXES-- CHEMICAL PREPARATION;NAPHTHALENE-- DERIVATIZATION;TITANIUM COMPLEXES-- CHEMICAL PREPARATION;ZIRCONIUM COMPLEXES-- CHEMICAL PREPARATION
Related SubjectAROMATICS;CHEMICAL REACTIONS;COMPLEXES;CONDENSED AROMATICS;HYDROCARBONS;ORGANIC COMPOUNDS;SYNTHESIS;TRANSITION ELEMENT COMPLEXES
Description/Abstract An alternative one-pot reaction to synthesize [K(15C5)[sub 2]][sub 2][M(CO)[sub 6]] has been developed by the reduction of MC[sub 4][center dot]2THF (M = Ti, Zr, Hf), in the presence of four equivalents 15-crown-5 or 15C5, with six equivalents of potassium naphthalenide radical anion followed by carbonylation.^Also, the previously unknown [K(15C5)[sub 2]][sub 2][Hf(CO)[sub 6]] was obtained by potassium naphthalenide promoted reductive carbonylations of HfCl[sub 4][center dot]2THF in the presence of PMe[sub 3]; [Hf(C[sub 10]H[sub 8])[sub 2]SnPh[sub 3]][sup 1[minus]] or [Hf(CO)[sub 5](SnPh[sub 3])][sup [minus]2].^The first zerovalent bis(naphthalene)group IV complexes have been stabilized as derivatives of the general formula [M(C[sub 10]H[sub 8])[sub 2]L][sup [minus]], where L = SnPh[sub 3], SnMe[sub 3], PPh[sub 2] or O[sup t]Bu.^A single crystal X-ray study of [Ti([eta][sup 4]-C[sub 10]H[sub 8])[sub 2]][sup [minus]2[minus]] has verified the presence of two [eta][sup 4]-C[sub 10]H[sub 8] naphthalene ligands in this complex.^The first isolable hexacarbonyltitanium(O) complexes, [K(15C5)[sub 2]](Ti(CO)[sub 6]SnR[sub 3])] (R = Cy, Ph, Me) have been synthesized by two independent methods.^These involved reductive carbonylation of TiCl[sub 4][center dot]2THF via [Ti(C[sub 10]H[sub 8])[sub 2]SnR[sub 3]][sup [minus]] were examined and indicated that these compounds could be useful precursors and act as synthetic equivalents` of the unknown Ti(CO)[sub 7].^The formulation of [K(15C5)[sub 2]][Ti(CO)[sub 6]SnCy[sub 3]] has been fully confirmed by multinuclear NMR spectroscopy and X-ray crystallography.^Carbonylation of the zerovalent bis(naphthalene) zirconium and hafnium compounds, [M(C[sub 10]H[sub 8])[sub 2]SnR[sub 3]][sup [minus]] (R = Me, Ph, provided new zerovalent bis-stannyl)carbonyl complexes of the general formula [M(CO)[sub 5](SnR[sub 3])[sub 2][sup 2[minus]] as its [K(15C5)[sub 2]][sup +] salt was confirmed by X-ray crystallography.
PublisherMinneapolis, MN (United States) ;Univ. of Minnesota
Country of PublicationUnited States
LanguageEnglish
FormatPages: (315 p)
AvailabilityUniversity Microfilms, P.O. Box 1764, Ann Arbor, MI 48106 (United States). Order No. 94-05,366
System Entry Date2001 May 13

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