Mononuclear Carbene Dithiolate [Ni(NHX)(′S2C ′)] Complexes with HNX = HNPiPr3 or HNSPh2 Coligands (′S2C ′ 2– = 1,3‐ImidazolidinylN,N′‐bis(2‐benzenethiolate)(2–)) |
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Authors: | Dieter Sellmann Franz Geipel Frank W. Heinemann |
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Abstract: | Cleavage reactions of the dinuclear [{Ni(′S2C ′)}2] · DMF (′S2C ′ 2– = 1,3‐imidazolidinyl‐N,N′‐bis(2‐benzenethiolate)(2–)) with HNPiPr3 or HNSPh2 yielded the mononuclear complexes [Ni(NHPiPr3)(′S2C ′)] ( 1 ) and [Ni(NHSPh2)(′S2C ′)] ( 2 ) which have been completely characterized. The nickel‐carbene‐dithiolate [Ni(′S2C ′)] moiety is one of the very rare complex fragments that are able to coordinate both HNPR3 or HNSR2. IR spectra and X‐ray structure determinations show that 1 and 2 exhibit intramolecular N–H…S(thiolate) hydrogen bonds. Geometric parameters and NMR spectroscopic data of 1 and 2 are compatible with N–X single bonds and ylidic structures of the HNPiPr3 and HNSPh2 ligands. Comparison of Ni–N distances in diamagnetic and paramagnetic [Ni(NHSPh2)] complexes was rendered possible through the X‐ray structure determination of the homoleptic [Ni(NHSPh2)6]Cl2 ( 3 ) which formed as minor by‐product in the synthesis of 2 . |
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Keywords: | Nickel Carbene complexes Hydrogen bond |
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