Less Is More: Three‐Coordinate C,N‐Chelated Distannynes and Digermynes |
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| Authors: | Miroslav Novák Marek Bou?ka Dr Libor Dostál Dr Ale? R??i?ka Dr Alexander Hoffmann Prof?Dr Sonja Herres‐Pawlis Dr Roman Jambor |
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| Affiliation: | 1. Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, 53210, Pardubice (Czech Republic);2. Institut für Anorganische Chemie, Rheinisch‐Westf?lische Technische Hochschule Aachen, Landoltweg 1,52074 Aachen (Germany) |
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| Abstract: | We report here the synthesis of new C,N‐chelated chlorostannylenes and germylenes L3MCl (M=Sn( 1 ), Ge ( 2 )) and L4MCl (M=Sn( 3 ), Ge ( 4 )) containing sterically demanding C,N‐chelating ligands L3, 4 (L3=2,4‐di‐tBu‐6‐(Et2NCH2)C6H2]?; L4=2,4‐di‐tBu‐6‐{(C6H3‐2′,6′‐iPr2)N=CH}C6H2]?). Reductions of 1 – 4 yielded three‐coordinate C,N‐chelated distannynes and digermynes L3, 4M ]2 for the first time ( 5 : L3, M=Sn, 6 : L3, M=Ge, 7 : L4, M=Sn, 8 : L4, M=Ge). For comparison, the four‐coordinate distannyne L5Sn]2 ( 10 ) stabilized by N,C,N‐chelate L5 (L5=2,6‐{(C6H3‐2′,6′‐Me2)N?CH}2C6H3]?) was prepared by the reduction of chlorostannylene L5SnCl ( 9 ). Hence, we highlight the role of donor‐driven stabilization of tetrynes. Compounds 1 – 10 were characterized by means of elemental analysis, NMR spectroscopy, and in the case of 1 , 2 , 5 – 7 , and 10 , also by single‐crystal X‐ray diffraction analysis. The bonding situation in either three‐ or four‐coordinate distannynes 5 , 7 , and 10 was evaluated by DFT calculations. DFT calculations were also used to compare the nature of the metal–metal bond in three‐coordinate C,N‐chelating distannyne L3Sn]2 ( 5 ) and related digermyme L3Ge]2 ( 6 ). |
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| Keywords: | coordination modes density functional calculations germanium main‐group chemistry NMR spectroscopy tin |
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