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Mononuclear Carbene Dithiolate [Ni(NHX)(′S 2 C ′)] Complexes with HNX = HNP i Pr 3 or HNSPh 2 Coligands (′S 2 C ′ 2– = 1,3‐Imidazolidinyl N,N ′‐bis(2‐benzenethiolate)(2–))
Author(s) -
Sellmann Dieter,
Geipel Franz,
Heinemann Frank W.
Publication year - 2001
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/1521-3749(200105)627:5<1034::aid-zaac1034>3.0.co;2-2
Subject(s) - chemistry , homoleptic , carbene , nickel , intramolecular force , moiety , stereochemistry , hydrogen bond , crystallography , nuclear magnetic resonance spectroscopy , medicinal chemistry , molecule , metal , catalysis , organic chemistry
Abstract Cleavage reactions of the dinuclear [{Ni(′S 2 C ′)} 2 ] · DMF (′S 2 C ′ 2– = 1,3‐imidazolidinyl‐ N,N ′‐bis(2‐benzenethiolate)(2–)) with HNP i Pr 3 or HNSPh 2 yielded the mononuclear complexes [Ni(NHP i Pr 3 )(′S 2 C ′)] ( 1 ) and [Ni(NHSPh 2 )(′S 2 C ′)] ( 2 ) which have been completely characterized. The nickel‐carbene‐dithiolate [Ni(′S 2 C ′)] moiety is one of the very rare complex fragments that are able to coordinate both HNPR 3 or HNSR 2 . IR spectra and X‐ray structure determinations show that 1 and 2 exhibit intra molecular 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 HNP i Pr 3 and HNSPh 2 ligands. Comparison of Ni–N distances in diamagnetic and paramagnetic [Ni(NHSPh 2 )] complexes was rendered possible through the X‐ray structure determination of the homoleptic [Ni(NHSPh 2 ) 6 ]Cl 2 ( 3 ) which formed as minor by‐product in the synthesis of 2 .