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Chemistry. 2012 Nov 19;18(47):15079-85. doi: 10.1002/chem.201202796. Epub 2012 Oct 11.

M4(CH2)4 cubane-type rare-earth methylidene complexes: unique reactivity toward unsaturated C-O, C-N, and C-S bonds.

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State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, Liaoning 116024, PR China.


The reactivity of the cubane-type rare-earth methylidene complex [Cp'Lu(μ(3)-CH(2))](4) (1, Cp' = C(5)Me(4)SiMe(3)) with various unsaturated electrophiles was investigated. The reaction of 1 with CO (1 atm) at room temperature gave the bis(ketene dianion)/dimethylidene complex [Cp'(4)Lu(4)(μ(3)-CH(2))(2)(μ(3),η(2)-O-C=CH(2))(2)] (2) in 86 % yield through the insertion of two molecules of CO into two of the four lutetium-methylidene units. In the reaction with the sterically demanding N,N-diisopropylcarbodiimide at 60 °C, only one of the four methylidene units in 1 reacted with one molecule of the carbodiimide substrate to give the mono(ethylene diamido)/trimethylidene complex [Cp'(4)Lu(4)(μ(3)-CH(2))(3) {iPrNC(=CH(2))NiPr}] (3) in 83% yield. Similarly, the reaction of 1 with phenyl isothiocyanate gave the ethylene amido thiolate/trimethylidene complex [Cp'(4)Lu(4)(μ(3)-CH(2))(3) {PhNC(S)=CH(2)}] (4). In the case of phenyl isocyanate, two of the four methylidene units in 1 reacted with four molecules of the substrate at ambient temperature to give the malonodiimidate/dimethylidene complex [Cp'(4)Lu(4)(μ(3)-CH(2))(2) {PhN=C(O)CH(2)(O)C=NPh}(2)] (5) in 87% yield. In this reaction, each of the two lutetium-methylidene bonds per methylidene unit inserted one molecule of phenyl isocyanate. All the products have been fully characterized by NMR spectroscopy, X-ray diffraction, and microelemental analyses.


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