Group 4 Metalloporphyrin Diolato Complexes and Catalytic Application Metalloporphyrins and Related Transition Metal Complexes.

Du, G.

Technical Information Center Oak Ridge Tennessee

关键词: Diolato complexes;    Catalysts;    Magnesium complexes;    Catalytic effects;    Chemical bonds;   

RP-ID  :  DE2005835301

学科分类：工程和技术（综合）

美国|英语

来源: National Technical Reports Library

【 摘 要 】

In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl(sub 2) (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti((eta)(sup 2)-PhC(triple-bond)CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti((eta)(sup 2)-PhC(triple-bond)CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti(O(Ph)(sub 2)C(Ph)(sub 2)O) to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti((eta)(sup 2)-PhC(triple-bond)CPh) with benzoin.