81097-96-3

Upstream product

• 14647-23-5 1,2-bis(diphenylphosphino)ethane nickel(II) chloride 
• 20433-73-2 [di-n-butyltin dicyanoethylene-1,2-dithiolate] 
• 1663-45-2 1,2-bis-(diphenylphosphino)ethane 

Relevant academic research and scientific papers

Planar Ni(II) 1,2-dithiolenes involving bidentate P-donor ligands

A series of planar Ni(II) dithiolenes derived of maleonitriledithiol (mnt), benzene-1,2-dithiol (bdt) and toluene-3,4-dithiol (tdt) with bidentate P,P-ligands (dppe = 1,2-bis(diphenylphosphino)ethane, dppp = 1,3-bis(diphenylphosphino)propane, dppb = 1,4-b

The synthesis and characterization of Ni, Pd and Pt maleonitriledithiolate complexes: X-ray crystal structures of the isomorphous Ni, Pd and Pt (Ph2PCH2CH2PPh 2)M(maleonitriledithiolate) congeners

The synthesis of a series of maleonitriledithiolate complexes of nickel, palladium and platinum phosphines having the formulae (dppe)M(mnt) and (Ph3P)2M(mnt) (where dppe = Ph2PCH2CH2PPh2, mnt = 1,2-dicyanoethene-1,2-dithiolate and M = Ni, Pd or Pt) from the reaction of Na2(mnt) and the appropriate (phosphine)MCl2 is reported. These complexes were characterized by a combination of mass spectrometry, IR, UV-Visible and 1H, 13C and 31P NMR spectroscopy. In addition, characterization of the title complexes by single crystal X-ray diffraction of all three congeners revealed them to be isomorphous. Analysis of the diffraction data reveals that the metal centers are all square planar, that the planar mnt ligands are tilted slightly away from the metal square planes, and that the mnt ligand is best described as a dithiolate rather than a dithione.

Star porphyrazines: Peripheral chelation of porphyrazineoctathiolate by diphosphinonickel ions

We have synthesized new pentametallic macrocyclic complexes based on the polynucleating ligand, porphyrazine2,3,7,8,12,13,17,18-octathiolate, (pzot)8-. This ligand can be thought of as a porphyrazine (tetraazaporphyrin) bearing four dithiolene moieties peripherally at the β-pyrrole positions, and we show that a transition-metal ion can be chelated to each of the four peripheral dithiolene moieties. The complexes [(P-P)Ni]4[Ni(pzot)] (2a, P-P = dppe; 2b, P-P = dppy; 2c, P-P = dppb; 2d, P-P = dcpe) have been synthesized and characterized. Complex 2a crystallizes in the orthorhombic space group Cmc1 (No. 36) with 4 macrocycles and 16 solvent molecules (A,T-dimethylformamide) in a unit cell of dimensions a = 24.630(5) A?, b = 20.607(4) A?, c = 30.675(6) A?, The [Ni(pzot)]8- ligand in 2a coordinates four Ni(P-P) moieties around its periphery with the two thiolate sulfur atoms of each pyrrole binding a nickel ion in a bidentate (S-S) coordination mode. This is in contrast to the reaction of [Ni(pzot)]8- with SnR2X2, which yielded Ni(pzot)(SnR2)4 (1), where each tin is coordinated in the tridentate (S-N-S) mode, with the thiolate sulfur atoms from two pyrroles and one m-nitrogen atom as ligands from the macrocycle (Vela?zquez, C. S.; Fox, G. A.; Broderick, W. E.; Andersen, K; Anderson, O. P.; Barrett, A. G. M; Hoffman, B. M. J. Am. Chem. Soc. 1992, 114,1416-7424). Comparison of the crystal structures of 1, 2a, and aquo(octakis(methylthio)porphyrazinato)magnesium(II) (Mg(omtp)), a structurally unconstrained reference compound with eight peripheral methylthio groups, shows that [Ni(pzot)]8- adjusts to accommodate either the (S-S) or (S-N-S) modes of coordinating the metal ions at the periphery by a swing of the Cβ-S bond. 1H and 31P NMR studies have been used to determine the nature of the coordination of the Ni(P-P) units to the [Ni(pzot)]8- macrocycle in solution. Model compounds were synthesized as structural references to mimic both possible coordination sites of the [Ni(pzot)]8- ligand. The 1H and 31P NMR chemical shifts of macrocycles 2a-d and their respective bidentate model complexes clearly indicate that the macrocycle in solution also binds the Ni(P-P) units in a bidentate fashion. The electronic absorption spectra of complexes 2a-d show a red-shift of the absorbance in the Q-band region due to interaction of the porphyrazine π-system with the four peripheral metal ions.

Spectroelectrochemistry of nickel complexes. Voltammetric and ESR studies of the redox reactions of phosphine-dithiolate and phosphine-catecholate complexes of nickel

The redox properties of nickel(II) complexes of the type [Ni(PPh3)2L]n+ (L = dithiolate (n = 0) or dithiocarbamate (n = 1)) and Ni(dpe)L (dpe = bis(diphenylphosphino)ethane, L = dithiolate or catecholate) have been studied by cyclic voltammetry at a platinum electrode, and the products of the redox reactions have been identified by electron spin resonance spectroscopy. All of these complexes show reversible or quasi-reversible one-electron reduction processes, and the reduction potentials for the PPh3 complexes are about 0.5 V higher than those of the corresponding dpe complexes. In the case of triphenylphosphine complexes such as Ni(PPh3)2((CN)2C2S2), the voltammetry shows evidence of a dissociation equilibrium involving loss of triphenylphosphine from the nickel species present after the electron-transfer process. The frozen-solution ESR spectra of the reduction products show large, anisotropic hyperfine coupling to two equivalent 31P nuclei and anisotropic g values characteristic of d9 nickel(I) species. The PPh3 complexes have smaller 31P hyperfine coupling constants than the corresponding dpe complexes. The 31P hyperfine coupling parameters have been analyzed for some representative complexes, and the amount of spin density transferred from the metal to the phosphine ligands has been estimated. In addition to the reduction process, the catecholate complexes undergo a reversible one-electron oxidation. The ESR spectra of the products of such oxidations show only a small 31P hyperfine coupling, hyperfine coupling to nuclei in the catecholate ligand, and almost isotropic g values. These species are therefore formulated as nickel(II) complexes containing coordinated semiquinone radical anions.