Synthesis and non-conventional structure of square-planar Pd(ii) and Pt(ii) complexes with an N, C, N-chelated stibinidene ligand. Issue 16 (12th April 2018)

• Record Type: Journal Article
• Authors: Kořenková, Monika; Hejda, Martin; Štěpnička, Petr; Uhlík, Filip; Jambor, Roman; Růžička, Aleš; Dostál, Libor
• Is Part Of: Dalton transactions. Volume 47:Issue 16(2018)
• Page Start: 5812
• Page End: 5822
• Publication Date: 2018-04-12
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt00714d
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Novel Sb(i )→Pd(ii ) and Sb(i )→Pt(ii ) complexes were shown to form rotamers in solution due to the side-on coordination of the stibinidene ligand. Abstract : The N, C, N -chelated stibinidene, ArSb (Ar = C6 H3 -2, 6-(CHN t Bu)2 ), reacts with Pt(ii ) compounds [PtCl2 L2 ] resulting in the formation of 1 : 1 complexes, cis -[PtCl2 L(ArSb)] (L = Me2 S (1 ), dmso (2 )). In contrast, attempts to synthesize similar Pd(ii ) complexes failed, resulting only in the formation of elemental palladium. To increase the stability of the ArSb complexes, in particular those containing Pd(ii ), the simple auxiliary ligands were replaced with C, N -chelating ones, which led to a set of four compounds of the type [RMCl(ArSb)], where R = C6 H4 -2-(CH2 NMe2 ) or Fe(η 5 -C5 H4 )(η 5 -C5 H3 -2-(CH2 NMe2 )) and M = Pd (3, 5 ) or Pt (4, 6 ). Compounds1–6 were characterized by 1 H and 13 C{ 1 H} NMR spectroscopy and single-crystal X-ray diffraction analysis, and in the case of ferrocene derivatives5 and6, also by cyclic voltammetry. Compounds2–6 were shown to form rotamers in solution due to the side-on coordination of the ArSb ligand and a hindered rotation around the Sb–Pd(Pt) bond. This process was investigated by 1 H-VT-NMR spectroscopy and by DFT computations.