Palladium(II) and Platinum(II) Bis(Stibinidene) Complexes with Intramolecular Hydrogen-Bond Enforced Geometries.

The coordination capability of two N,C,N pincer coordinated stibinidenes, i. e. bis(imino)- [2,6-(DippN=CH)2 C6 H3 ]Sb (1) or imino-amino- [2-(DippN=CH)-6-(DippNHCH2 )C6 H3 ]Sb (2) toward palladium(II) and platinum(II) centers was examined. In the course of this study, seven new square-planar bis(stibinidene) complexes were synthesized and characterized by NMR, IR, Raman, UV-vis spectroscopy and single crystal (sc)-X-ray diffraction analysis. In all cases, both stibinidene ligands 1 or 2 adopt trans positions, but differ significantly in the torsion angle describing mutual orientation of aromatic rings of the stibinidenes along the Sb-Pd/Pt-Sb axes. Furthermore, majority of complexes form isomers in solution most probably due to a hindered rotation around Sb-Pd/Pt bonds caused by bulkiness of 1 and 2. This phenomenon also seems to be influenced by the absence/presence of a pendant -CH2 NH- group in 1/2 that is able to form intramolecular hydrogen bonds with the adjacent chlorine atom(s) attached to the metal centers. The whole problem was subjected to a theoretical study focusing on the role of hydrogen bonds in structure architecture of the complexes. To describe the UV-vis spectra of these highly coloured complexes, TD-DFT calculations were employed. These outline differences between the stibinidene ligands, the transition metals as well as between the charge of the complexes (neutral or anionic).

Oxidations of N-coordinated Arsinidene and Stibinidene by Substituted Quinones: A Remarkable Follow-Up Reactivity.

The reactivity of pnictinidenes [2-(DippN=CH)-6-(DippNHCH2 )C6 H3 ]E (where E=As (1) or Sb (2)) toward substituted ortho- and para-quinones is reported. The central pnictogen atom is easily oxidized by ortho-quinones closing five-membered EO2 C2 ring. The oxidized antimony derivatives are stable species, while in the case of arsenic compounds the hydrogen of the pendant amino NHCH2 group cleaves one newly formed As-O bonds leading to the closure of a new azaarsole ring. Furthermore, a heating of these arsenic heterocycles resulted in a C-H bond activation at the NCH2 group involved in this heterocycle followed by a reductive elimination of corresponding catechols and arsinidene [2,6-(DippN=CH)C6 H3 ]As. Using of para-quinones, resulted in the oxidation of the central atom with a concomitant hydrogen migration from NHCH2 group even in the case of the antimony derivatives. The reductive elimination of hydroquinones is in this case feasible for all compounds. Studied compounds were characterized by multi-nuclear NMR, IR and Raman spectroscopy and single-crystal X-ray diffraction analysis. The theoretical study focusing the key compounds and reactions is also included.

Beyond simple hetero Diels-Alder cycloadditions. A new type of element-ligand cooperativity at N,C,N-coordinated arsinidene and stibinidene centres in the reaction with an electron-deficient alkyne.

The reactivity of two types of organopnictogen(I) N,C,N-pincer ligand coordinated compound, i.e. [2,6-(DippNCH)2C6H3]E (1-E, where E = As, Sb, Bi; Dipp = 2,6-iPrC6H3) and [2-(DippNCH)-6-(DippNHCH2)C6H3]E (6-E, where E = As or Sb), toward an electron-deficient alkyne, i.e. dimethyl acetylenedicarboxylate (DMAD), is reported. All reactions represent remarkable examples of element-ligand cooperation (ELC). In the first step, all compounds react via dearomatization of a latent heteropnictole ring producing rare examples of hetero Diels-Alder (DA) adducts. These compounds then smoothly convert to 1-arsanaphthalenes via hydrogen migration, thereby recovering the aromatic 10π-electron system. Furthermore, in the case of bis(imino) derivatives of 1-E, heating of DA adducts in pyridine led to a hydrogenation of the triple bond of DMAD with the concomitant recovery of the univalent pnictinidene centre, which is in turn able to activate the second molecule of DMAD. In contrast, the non-symmetric derivative of 6-As upon heating in pyridine produced bicyclic trivalent arsenic compounds as a result of an attack of the pendant secondary NH group into the arsa-heterocyclic system. For 6-Sb, a remarkable stoichiometric hydrogenation of the DMAD molecule was observed by NMR spectroscopy involving the reductive elimination of dimethylfumarate in the final step of the reaction sequence. The whole study is accompanied by a theoretical survey that describes the main thermodynamic parameters of the reported reactions and explains the reaction pathways observed in the experiments.

Coordination capabilities of bis-(2-pyridyl)amides in the field of divalent germanium, tin and lead compounds.

The reactivity of two lithium amides derived from bis-(2-pyridyl)amine (dpa)H or its methyl-substituted congener bis-(6-methyl-2-pyridyl)amine (Me-dpa)H, i.e. (dpa)Li (1) and (Me-dpa)Li (2), toward ECl2 (where E = Ge (dioxane complex) and Sn) is reported. This study produced both heteroleptic complexes (dpa)GeCl (3), [(dpa)SnCl]2 (4), and (Me-dpa)GeCl (5) and homoleptic complexes (dpa)2E (E = Ge (6) or Sn (7)) and (Me-dpa)2E (E = Ge (8) or Sn (9)). The structures of all complexes were established by single-crystal X-ray diffraction analysis showing significant differences depending on the E atom and ligand used. By contrast, in solution, the majority of compounds showed a fluxional behaviour as demonstrated by the NMR study. Finally, it turned out that the Me-dpa ligand, unlike dpa, is able to form ate complexes [(Me-dpa)3E]Li (E = Ge (10), Sn (11) or Pb (12)), whose structures were determined by single-crystal X-ray diffraction analysis. This study revealed the formation of two isomers for Ge and Sn complexes depending on the coordination preference of the lithium atom being coordinated either by nitrogen donors (10-12) or solely by the Ge or Sn electron lone pair (10a and 11a). Furthermore, the NMR experiments proved that the germanium complex 10 exhibits only limited stability in solution and decomposes to germylene 8 and lithium amide 2.