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Diphosphorus Release and Heterocumulene Oligomerisation by Nickel Complexes

ABSTRACT: Abstract The generation of diphosphorus molecules P2 under mild conditions in solution is a useful strategy to generate diphosphines via [4+2] cycloadditions. We recently described the release of P2 units from the nickel butterfly complex [{(IMes)Ni(CO)}2(μ2,η2:η2‐P2)] (IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazolin‐2‐ylidene) upon addition of CO gas. Herein, we developed an alternative protocol for the same process using heterocumulenes. In addition to formation of P4 (the dimerisation product of P2), the reactions afford nickel complexes of novel pincer‐type ligands. Aryl isothiocyanates undergo a trimerisation within the coordination sphere of nickel and afford square planar nickel complexes with S−C−S pincer‐ligand frameworks. Carbon disulfide coordinates to the [(IMes)Ni]‐fragment in an η2‐fashion, affording a dinuclear complex. Similar products are formed when the N‐heterocyclic carbene nickel(0) complex [(IMes)Ni(vtms)2] is used as a precursor (vtms=vinyltrimethylsilane). The reactivity of a nickel‐phosphorus butterfly complex toward tetramethylcarbene and heterocumulenes was investigated. While the reaction with the carbene resulted in retention of the Ni2P2 core, reactions with isothiocyanates or carbon disulfide afforded phosphorus‐free complexes with S−C−S pincer ligands. The same complexes were also isolated using a nickel(0) alkene complex as a precursor.

SUBMITTER: Hierlmeier G

PROVIDER: S-EPMC9314841 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:A trinuclear nickel complex of phenanthrene-9,10-dione dioxime (H2pqd), namely bis-[μ2-9,10-bis-(oxido-imino)-phenanthrene]-bis-[μ2-10-(oxido-imino)phenanthrene-9-one oxime](phenanthrene-9,10-dione dioxime)trinickel(II) toluene disolvate, [Ni3(C14H8N2O2)2(C14H9N2O2)2(C14H10N2O2)]·2C7H8, has been isolated and its crystal structure determined. This complex features three independent Ni(II) atoms that are arranged in a triangular fashion along with five supporting ligands. There are two square-planar Ni(II) atoms and a third pseudo-octa-hedral Ni(II) atom. While the square-planar Ni(II) atoms are stacked, there are no ligand bridges between them. Each square-planar Ni(II) atom, however, bridges with the pseudo-octa--hedral Ni(II) atom through Ni-N-O-Ni and Ni-O-Ni bonds. A fluorido-bor-ation reaction of the proton-bridged species gave the analogous complex bis-(μ2-bis-{[10-(oxido-imino)-9,10-di-hydro-phenanthren-9-yl-idene]amino}di-fluorido-borato)(phenanthrene-9,10-dione dioxime)trinickel(II) dichloromethane trisolvate, [Ni3(C28H16BF2N4O2)4(C14H10N2O2)]·3CH2Cl2, which shows the same binding structure, but features a widened Ni-Ni inter-action between the square-planar Ni(II) atoms. The proton-bridged complex completes the macrocyclic coordination around the square-planar Ni(II) atoms by means of an O-H⋯O hydrogen bond. Both compounds feature O-H⋯N hydrogen bonds between the oxime and the N atoms attached to square-planar nickel atom. The nickel units show no direct inter-action with their nearest neighbors in the extended lattice. Two π-stacking inter-actions between adjacent mol-ecules are found: one with a centroid-centroid distance of 3.886 (2) Å and the other with a centroid-centroid distance of 4.256 (3) Å. In the latter case, although not aromatic, the distance to the centroid of the central phenanthrene ring is shorter, with a distance of 3.528 (3) Å. Toluene mol-ecules occupy the solvent channels that are oriented along the c axis. In the fluorido-boronate structure, the solvent (DCM) was too badly disordered to be modelled, so its contribution was removed using SQUEEZE [Spek (2015 ▸). Acta Cryst. C71, 9-18].

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Diphosphorus Release and Heterocumulene Oligomerisation by Nickel Complexes

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