Synthesis of a Molybdenum Hydrido(hydrogermylene) Complex and Its Conversion to a Germylyne Complex: Another Route through Dehydrogenation with Nitriles
A molybdenum germylene complex having Mo–H and Ge–H bonds, Cp*(CO)2(H)MoGe(H){C(SiMe3)3} (1), was synthesized by the reaction of a methyl molybdenum complex with a trihydrogermane and was converted to a germylyne complex, Cp*(CO)2MoGe{C(SiMe3)3} (2), via dehydrogenation with aryl isocyanat...
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Published in | Organometallics Vol. 39; no. 23; pp. 4350 - 4361 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
American Chemical Society
14.12.2020
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Online Access | Get full text |
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Summary: | A molybdenum germylene complex having Mo–H and Ge–H bonds, Cp*(CO)2(H)MoGe(H){C(SiMe3)3} (1), was synthesized by the reaction of a methyl molybdenum complex with a trihydrogermane and was converted to a germylyne complex, Cp*(CO)2MoGe{C(SiMe3)3} (2), via dehydrogenation with aryl isocyanates under mild heating. A similar conversion from the same germylene complex into the germylyne complex also occurred using nitriles instead of isocyanates, while releasing imines via a Mo–Ge–N three-membered ring complex Cp*(CO)2Mo[κ2(N,Ge)Ge-(NCHR){C(SiMe3)3}] (4, R = Me and aryl groups) as an intermediate. Formation of imines was confirmed by a trapping experiment with BPh3, which afforded a BPh3-imine adduct. In the case of aryl nitriles, the corresponding three-membered ring intermediates were converted into the germylyne complex efficiently by blue LED light irradiation. TD-DFT calculations on the three-membered-ring intermediate suggest that the role of the LED light is to induce CO ligand dissociation from the intermediate via a metal-to-ligand-charge-transfer (MLCT) transition. |
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ISSN: | 0276-7333 1520-6041 |
DOI: | 10.1021/acs.organomet.0c00518 |