(4,0)-Dirhodium(II) tetrakis[methyl 1-acetyl-2-oxoimidazolidine-4( S)-carboxylate]. Implications for the mechanism of ligand exchange reactions

The preparation and structural characterization of an elusive geometrical isomer of dirhodium(II) tetrakis[methyl 1-acetyl-2-oxoimidazolidine-4( S)-carboxylate], Rh 2(4 S-MACIM) 4, has been achieved. The imidazolidinone ligands are arrayed around the dirhodium(II) core with four nitrogen donor atoms...

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Bibliographic Details
Published in:Inorganica Chimica Acta 1997-12, Vol.266 (1), p.13-18
Main Authors: Doyle, Michael P., Raab, Conrad E., Roos, Gregory H.P., Lynch, Vincent, Simonsen, Stanley H.
Format: Article
Language:English
Subjects:
Carboxamidate complexes
Crystal structures
Cyclopropanation
Dinuclear complexes
Rhodium complexes
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Summary:The preparation and structural characterization of an elusive geometrical isomer of dirhodium(II) tetrakis[methyl 1-acetyl-2-oxoimidazolidine-4( S)-carboxylate], Rh 2(4 S-MACIM) 4, has been achieved. The imidazolidinone ligands are arrayed around the dirhodium(II) core with four nitrogen donor atoms bound to one rhodium and four oxygens bound to the other (4,0). The crystal structure of this compound has been determined to be that of (4,0)-Rh 2(4 S-MACIM) 4(CH 3 CN) 2 d( CH 3 CN): space group P2( in1) with cell constants a = 11.518(4), b = 16.851(2), c = 11.573(3) A ̊ , V = 2155.4(6) A ̊ 3, Z = 2,R = 0.0295, RhRh distance = 2.4547(6) A ̊ . Prepared by ligand substitution on Rh 2(OAc) 4, (4,0)-Rh 2(4 s-MACIM) 4 was isolated in 25% yield, but this compound isomerizes to its (2,2- cis)- and (3,1)-isomers under the reaction conditions. Racemic products were obtained from catalytic uses of (4,0)-Rh 2(4 S-MACIM) 4 in diazo decomposition reactions.
ISSN:0020-1693
1873-3255
DOI:10.1016/S0020-1693(97)05525-4