Highly reduced organometallics of the Group IV elements: Part One. The study of (trmpe) metal tetracarbonyl complexes of titanium, zirconium, and hafnium. Part Two. The study of bis-arene titanium complexes prepared from arene radical anions

Miscellaneous · Wed Jan 01 00:00:00 EST 1992

OSTI ID:5720222

Blackburn, D W

Potassium naphthalenide reduction of solutions of the Group IV transition metal salts MCl[sub 4][center dot]THF, M = Ti, Zr, and Hf, in the presence of the tridentate phosphine ligand 1,1,1-tris(dimethylphosphinomethyl)ethane (trmpe), at -70[degrees] under Ar, followed by carbonylation at atmospheric pressure, provides the zerovalent carbonylphosphine complexes M(CO)[sub 4](trmpe). Yields range from 5% for Hf to 50% for Ti. The complexes were characterized by [sup 31]P and [sup 13]C NMR studies, and the Zr complex additionally by X-ray crystallography. The titanium complex reacts with triphenylstannide to displace one carbon monoxide ligand, forming the [(trmpe)Ti(CO)[sub 3](Sn(C[sub 6]H[sub 5])[sub 3])] anion. The reduction of TiCl[sub 4][center dot]2THF with arene radical anions provides bis-arene sandwich complexes in high yield (80-95%). For arene = naphthalene, the 18-electron [Ti(C[sub 10]H[sub 8])[sub 2]][sup 2[minus]] complex could be isolated in pure form as the bis(15-crown-5) potassium salt. For arene = biphenyl, the product is the radical [Ti(C[sub 12]H[sub 10])[sub 2]][sup [minus]]. Oxidation of the bis-biphenyl titanium anion with I[sub 2] gives the 16-electron, zerovalent complex Ti(C[sub 12]H[sub 10])[sub 2]. The arene (4,4[prime] di-tert-butyl)biphenyl (dtBB) could be used to synthesize the salt [K(Crypt-2.2.2)][Ti(dtBB)[sub 2]] and the neutral complex Ti(dtBB)[sub 2]. Carbonylation of a cold THF Solution of [K(15-crown-5)[sub 2]] [Ti(C[sub 12]H[sub 10])[sub 2]] provides the salt of [Ti(CO)[sub 6]][sup 2[minus]]. Reduction of TiCl[sub 4][center dot]2THF with four equivalents of naphthalene radical anion generates a thermally unstable complex, formulated as Ti(C[sub 10]H[sub 8])[sub 2], which was characterized by its reaction with [Sn(C[sub 6]H[sub 5])[sub 3]][sup [minus]] and carbon monoxide to generate the known [Ti(CO)[sub 5](Sn(C[sub 6]H[sub 5])[sub 3])[sub 2]][sup 2[minus]]. This complex was also used to synthesize (trmpe)Ti(C[sub 10]H[sub 8]).

• Research Organization: Minnesota Univ., Minneapolis, MN (United States)
• OSTI ID: 5720222
• Resource Relation: Other Information: Thesis (Ph.D.)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
HAFNIUM COMPLEXES
REDUCTION
ORGANOMETALLIC COMPOUNDS
CHEMICAL REACTIONS
TITANIUM COMPLEXES
ZIRCONIUM COMPLEXES
ANIONS
CARBONYLATION
CHEMICAL REACTION YIELD
CRYSTALLOGRAPHY
NUCLEAR MAGNETIC RESONANCE
RADICALS
CHARGED PARTICLES
COMPLEXES
IONS
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
RESONANCE
TRANSITION ELEMENT COMPLEXES
YIELDS
400200* - Inorganic
Organic
& Physical Chemistry
360600 - Other Materials