Facile and Room-Temperature Activation of C_sp3–Cl Bonds by Cheap and Air-Stable Nickel(II) Complexes of (<i>N</i>‑Thioether) DPPA-Type Ligands

Reaction of the diphosphine (<i>P</i>,<i>P</i>) ligand N­(PPh₂)₂(<i>n-</i>PrSMe) (<b>1</b>) or N­(PPh₂)₂(<i>p</i>-(SMe)­C₆H₄) (<b>2</b>) with [Ni­(NCMe)₆]­[BF₄]₂ in a 2:1 molar ratio afforded the bis-chelated, dicationic Ni­(II) complexes [Ni­(<b>1</b>)₂]­[BF₄]₂ (<b>3</b>) and [Ni­(<b>2</b>)₂]­[BF₄]₂ (<b>4</b>), respectively. Both complexes were characterized in solution by various spectroscopic techniques and in the solid state by X-ray diffraction studies. In the presence of Zn metal used as cheap reductant, complexes <b>3</b> and <b>4</b> activate the inert C–Cl bonds of dichloromethane at room temperature to afford in high yield the phosphonium ylide derivatives [Ni­((Ph₂P)­N­{P­(CH₂)­Ph₂}­(<i>n-</i>PrSMe)-<i>P</i>,<i>C</i>)₂]­[BF₄]₂ (<b>5</b>) and [Ni­((Ph₂P)­N­{P­(CH₂)­Ph₂}­(<i>p-</i>(SMe)­C₆H₄)-<i>P</i>,<i>C</i>)₂]­[BF₄]₂ (<b>6</b>), respectively. The formation of [Ni­((Ph₂P)­N­{P­(CH₂)­Ph₂}­(<i>n-</i>PrSMe)-<i>P</i>,<i>C</i>)₂]­Cl₂ (<b>5</b>′), an analogue of complex <b>5</b>, from a Ni(0) precursor supports the reduction of the Ni­(II) precursors by the Zn reagent prior to C–Cl bond activation. The structures of <b>5</b> and <b>5</b>′ were unambiguously established by X-ray diffraction analysis

Synthesis and Structural Characterizations of New Coordination Polymers Generated by the Interaction Between the Trinuclear Triangular SBU [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ and 4,4′-Bipyridine. 3°

The reactions of 4,4′-bipyridine with selected trinuclear triangular copper­(II) complexes, [Cu₃(μ₃-OH)­(μ-pz)₃(RCOO)₂L_<i>x</i>], [pz = pyrazolate anion, R = CH₃(CH₂)_<i>n</i> (2 ≤ <i>n</i> ≤ 5); L = H₂O, MeOH, EtOH] yielded a series of 1D coordination polymers (CPs) based on the repetition of [Cu₃(μ₃-OH)­(μ-pz)₃] secondary building units joined by bipyridine. The CPs were characterized by conventional analytical methods (elemental analyses, ESI-MS, IR spectra) and single crystal XRD determinations. An unprecedented 1D CP, generated through the bipyridine bridging hexanuclear copper clusters moieties, two 1D CPs presenting structural analogies, and two monodimensional tapes having almost exactly superimposable structures, were obtained. In one case, the crystal packing makes evident the presence of small, not-connected pores, accounting for ca. 6% of free cell volume