Structure and reactivity of organometallic intercalation compounds

Thesis/Dissertation · Wed Jan 01 04:00:00 EST 1992

OSTI ID:7205347

Lee, C F.H.

Intercalation of organometallic compounds into the layered metal phosphates, M(HPO[sub 4])[sub 2][center dot]H[sub 2]O has been restricted to only a few metallocenes. The authors have shown that organometallic carbonyl complexes can also be intercalated into [alpha]-Zr(HPO[sub 4])[sub 2][center dot]H[sub 2]O, ZrP. These intercalation compounds can be used to study the reactivity of the organometallic complex with the surface of the host lamellae, thus serving as models of surface reactions. In addition, these organometallic intercalation compounds may also be developed as potential heterogeneous catalysts. The synthesis and reactivity of two organometallic carbonyl intercalation compounds is presented. The guests, ([eta][sup 6]-phenethylamine)Cr(CO)[sub 3], CrNH[sub 2], and [(CO)[sub 3]Mn([eta][sub 5]-C[sub 5]H[sub 3] (CH[sub 3])CH[sub 2]-)][sub 2]NH, Mn[sub 2]NH, intercalate as bilayers into ZrP, with layer spacings of 22.3 [angstrom] and 20.2 [angstrom], respectively. Photolysis of the chromium intercalation compound, CrNH[sub 2][center dot]ZrP, results in different products, depending on the solvent. Photolysis of CrNH[sub 2][center dot]ZrP inbedded in a KBr matrix produces Cr(CO)[sub 5](phosphinol). In the absence of KBr, photolysis of CrNH[sub 2][center dot]ZrP followed by air oxidation results in the loss of the carbonyl ligands to form a carbonyl-free species, [beta]-Cr[center dot]ZrP. Thermal treatment of this sample generates [alpha]-Cr[center dot]P, which consists of crystallites of antiferromagnetic [alpha]-Cr[sub 2]O[sub 3]. Photolysis of the manganese intercalation compound, Mn[sub 2] NH[center dot]ZrP, proceeds with step-wise loss of the carbonyl ligands. The intermediate, A, is a CpMn(CO)[sub 2] (phosphinol) complex. The final photolytic product, B, is a high-spin, d[sup 5] CpMn(II) compound which is supported on the surface of the ZrP lamellae. Compound B is amorphous and has been found to produce saturated hydrocarbons from synthesis gas.

• Research Organization: Princeton Univ., NJ (United States)
• OSTI ID: 7205347
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360602 -- Other Materials-- Structure & Phase Studies
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL REACTIONS
CHROMIUM COMPOUNDS
CLATHRATES
MANGANESE COMPOUNDS
MOLECULAR STRUCTURE
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXYGEN COMPOUNDS
PHOSPHATES
PHOSPHORUS COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
ZIRCONIUM COMPOUNDS
ZIRCONIUM PHOSPHATES