The first metal complexes of the proton sponge 1,8-bis(N,N,N′,N′-tetramethylguanidino)naphthalene: syntheses and properties
In this work we report on the syntheses and properties of the first transition metal complexes of the proton sponge 1,8-bis(N,N,N′,N′-tetramethylguanidino)naphthalene (btmgn). Of the three complexes [(btmgn)PdCl2], [(btmgn)PtCl2] and [(btmgn)PtCl2(C2H4)], the first two feature a chelating btmgn liga...
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| Main Authors: | , , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
2008
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| In: |
European journal of inorganic chemistry
Year: 2008, Issue: 28, Pages: 4440-4447 |
| ISSN: | 1099-0682 |
| DOI: | 10.1002/ejic.200800677 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/ejic.200800677 Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/ejic.200800677 
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| Author Notes: | Ute Wild, Olaf Hübner, Astrid Maronna, Markus Enders, Elisabeth Kaifer, Hubert Wadepohl, and Hans-Jörg Himmel |
| Summary: | In this work we report on the syntheses and properties of the first transition metal complexes of the proton sponge 1,8-bis(N,N,N′,N′-tetramethylguanidino)naphthalene (btmgn). Of the three complexes [(btmgn)PdCl2], [(btmgn)PtCl2] and [(btmgn)PtCl2(C2H4)], the first two feature a chelating btmgn ligand that is bound to the metal atom through two nitrogen atoms. Only one metal-N bond is established in [(btmgn)PtCl2(C2H4)]. The molecular structures of [(btmgn)PdCl2] and [(btmgn)PtCl2] show some interesting details. X-ray crystallographic studies reveal that the naphthyl aromatic systems in both complexes are not planar, the metal atoms reside above the “best-plane” of the naphthyl systems and the compounds adopt a chiral conformation in the crystalline phase. Several dynamic processes of the two guanidinyl groups in solution were identified by line-shape analysis of the temperature-dependent NMR spectra. The complex [(btmgn)PtCl2(C2H4)] eliminates ethylene at elevated temperature to give [(btmgn)PtCl2]. Quantum chemical (DFT) calculations indicate that the ΔG0 value for this reaction is close to zero. Indeed the compound [(btmgbp)PtCl2] btmgbp = 2,2′-bis(N,N,N′,N′-tetramethylguanidino)biphenyl in which the naphthyl group is replaced by a biphenyl group is not amenable to ethylene elimination. First experiments point to interesting catalytic properties of the new complexes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) |
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| Item Description: | Die "N" im Ausdruck "N,N,N′,N′-tetramethylguanidino" sind im Titel kursiv dargestellt Published online: August 26, 2008 Gesehen am 24.11.2022 |
| Physical Description: | Online Resource |
| ISSN: | 1099-0682 |
| DOI: | 10.1002/ejic.200800677 |