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

Miscellaneous · Fri Jan 01 00:00:00 EST 1993

OSTI ID:7288352

Yuen, Pong Kau

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.

• Research Organization: Minnesota Univ., Minneapolis, MN (United States)
• OSTI ID: 7288352
• Resource Relation: Other Information: Thesis (Ph.D.)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
CHEMICAL PREPARATION
HAFNIUM COMPLEXES
NAPHTHALENE
DERIVATIZATION
TITANIUM COMPLEXES
ZIRCONIUM COMPLEXES
AROMATICS
CHEMICAL REACTIONS
COMPLEXES
CONDENSED AROMATICS
HYDROCARBONS
ORGANIC COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties