Synthesis, structure, and reactivity of alkoxide-based yttrium and lanthanide complexes

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

OSTI ID:6930785

Golden, R E

The reactivity of the prototypical trimetallic lanthanum tert-butoxide complex, La[sub 3]([mu][sub 3]-OCMe[sub 3])[sub 2]([mu]-OCMe[sub 3])[sub 3](OCMe[sub 3])[sub 4](THF)[sub 2], 1, with reagents such as phenylisocyanate, [AlMe[sub 3]][sub 2], and [Cu (OCMe[sub 3])][sub 4] was investigated. Compound 1 catalyzed the synthesis of PhN(H)C(O)OCMe[sub 3] from HOCMe[sub 3] and PhNCO and catalyzed the trimerization of PhNCO. Reaction of 1 with [AlMe[sub 3]][sub 2] resulted in formation of monolanthanum complex La([mu]-OCMe)[sub 3]([mu]-Me)[sub 3](AlMe[sub 2])[sub 3], 4. Examination of the reaction of LaCl[sub 3] with 4.5 equivalents of NaOC[sub 6]H[sub 4]Me-4 revealed an extensive chemistry for the pentametallic complex La[sub 2]Na[sub 3]([mu][sub 4]-OC[sub 6]H[sub 4]Me-4)[sub 3]([mu]-OC[sub 6]H[sub 4]Me-4)[sub 9](THF)[sub 5], 7, which contained a [mu][sub 4]-aryloxide. Compound 7 reacted with copper and nickel complexes to form adducts. Decomposition of 7 in THF/hexane and [NMe[sub 4]][La[sub 2]Na[sub 2]-(OC[sub 6]H[sub 4]Me-4)[sub 9](THF)[sub 5]], 10, in DME generated the unsolvated and solvated NaOC[sub 6]H[sub 4]Me-4 complexes [NaOC[sub 6]H[sub 4]Me[sub 4]][sub n], 6 and [Na(OC[sub 6]H[sub 4]Me-4)(DME)][sub 4], 11 respectively. A comparison of siloxide versus alkoxide ligands was made by studying triphenylsiloxide, OSiPh[sub 3], and triphenyl-methoxide, OCPh[sub 3], with yttrium and the lanthanides. Alcoholysis of Ln[N(SiMe[sub 3])[sub 2]][sub 3] (Ln = La, Ce, Y) with three equivalents of HOEPh[sub 3] (E = C, Si) in toluene formed unsolvated, dimeric compounds of the formula [Ln(OEPh[sub 3])[sub 2]([mu]-OEPh[sub 3])][sub 2]. the unsolvated OSiPh[sub 3] complexes react with THF to form monometallic, tri-solvated complexes Ln(OSiPh[sub 3])[sub 3](THF)[sub 3]. In contrast, the OCPh[sub 3] ligand forms disolvated Y(OCPh[sub 3])[sub 2](THF)[sub 2], 24. The synthesis of mixed-ligand complexes of empirical formula [open quotes]Ln (OR)[sub 2]Cl[close quotes], was studied.

• Research Organization: California Univ., Irvine, CA (United States)
• OSTI ID: 6930785
• Resource Relation: Other Information: Thesis (Ph.D.)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKOXIDES
ACTIVATION ENERGY
CHEMICAL PREPARATION
STRUCTURAL CHEMICAL ANALYSIS
RARE EARTH COMPLEXES
YTTRIUM COMPLEXES
CHEMICAL PROPERTIES
LIGANDS
COMPLEXES
ENERGY
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties