Chemistry of (octaethylporphyrinato)lutetium and -yttrium complexes: Synthesis and reactivity of (OEP)MX derivatives and the selective activation of O[sub 2] by (OEP)Y([mu]-Me)[sub 2]AlMe[sub 2]

Journal Article · Wed Dec 25 04:00:00 EST 1991 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00026a023· OSTI ID:6837223

Schaverien, C J ^[1]; Orpen, A G ^[2]

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1. Koninklijke/Shell Laboratorium, Amsterdam (Netherlands)
2. Univ. of Bristol (United Kingdom)

Reaction of ML[sub 3] (M = Lu, Y; L = CH(SiMe[sub 3])[sub 2], O-2,6-C[sub 6]H[sub 3][sup t]Bu[sub 2]) with octaethylporphyrin (OEPH[sub 2]) affords (OEP)ML complexes [M = Lu (1a), Y (1b), L = CH(SiM[sub 3])[sub 2]; M = Lu (2a), Y (2b), L = O-2,6-C[sub 6]H[sub 3][sup t]Bu[sub 2]]. The crystal structure of (OEP)LuCH(SiMe[sub 3])[sub 2] (1a) shows a highly dished porphyrin skeleton with the square-pyramidal, five coordinate lutetium atom 0.918 [angstrom] out of the N[sub 4] plane of the porphyrin ligand. Alkyl species 1 undergo facile protonolysis with HO-2,6-C[sub 6]H[sub 3][sup t]Bu[sub 2], HCC[sup t]Bu, or H[sub 2]O to give monomeric alkoxide, dimeric alkynyl, and dimeric hydroxide species [(OEP)MX][sub n] (n = 1,2) [M = Lu, Y; X = O-2, 6-C[sub 6]H[sub 3][sup t]Bu[sub 2] (2a,b), CC[sup t]Bu (3a,b), OH (4a,b)], respectively. Titration of (OEP)M([mu]-OH)[sub 2]M-(OEP) (4) with H[sub 2]O affords water adducts (OEP)M([mu]-OH)[sub 2](H[sub 2]O)[sub x]M(OEP). In marked contrast to the facile hydrogenation of Ln(C[sub 5]Me[sub 5])[sub 2]CH(SiMe[sub 3])[sub 2], alkyl species 1 do not undergo [sigma]-bond metathesis with H[sub 2] (20 atm, 25C, C[sub 6]D[sub 12]). Treatment with AlMe[sub 3] (2 equiv) in hexane yields monomeric, highly fluxional (OEP)Y([mu]-Me)[sub 2]AlMe[sub 2] (6), which selectively activates O[sub 2] to afford (OEP)Y([mu]-OMe)[sub 2]AlMe[sub 2] (7).

• OSTI ID: 6837223
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:26; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CARBOXYLIC ACIDS
CHEMICAL ACTIVATION
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
ELEMENTS
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
LUTETIUM COMPLEXES
MAGNETIC RESONANCE
NONMETALS
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXYGEN
PORPHYRINS
RARE EARTH COMPLEXES
RESONANCE
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION
YTTRIUM COMPLEXES