152276-94-3Relevant academic research and scientific papers
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
Landis, Katy G.,Hunter, Allen D.,Wagner, Timothy R.,Curtin, Larry S.,Filler, Francesca L.,Jansen-Varnum, Susan A.
, p. 155 - 162 (1998)
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.
Luminescent diphosphine dithiolate complexes of platinum(II): Synthesis, characterization, and structure
Bevilacqua, Joanne M.,Zuleta, Juan A.,Eisenberg, Richard
, p. 258 - 266 (2008/10/08)
The synthesis, characterization, and emission properties of a series of Pt(diphosphine)(dithiolate) complexes are reported. Diphosphine ligands include 1,2-bis(diphenylphosphino)ethane (dppe), 1,2-bis(diphenylphosphino)ethylene (dppv), 1,2-bis(diphenylphosphino)benzene (dppb), 1,2-bis(dicyclohexylphosphino)ethane (chpe), bis(diphenylphosphino)methane (dppm), 1,2-bis(dimethoxyphosphino)ethane (pompom), triphenylphosphine (PPh3), dimethylphenylphosphine (PMe2Ph), tricyclohexylphosphine (PCy3), triphenyl phosphite (P(OPh)3), and triisopropyl phosphite (P(O-i-Pr)3). Dithiolate ligands include maleonitriledithiolate (mnt) and 1-(ethoxycarbonyl)-1-cyanoethylene-2,2-dithiolate (ecda). The complexes are readily synthesized by the addition of the diphosphine ligand to Pt(COD)(dithiolate). On the basis of characterizations using NMR and infrared spectroscopies, all of the complexes are assigned square planar coordination geometries with varying degrees of distortion determined by ligand steric and electronic effects. The assignment of square planar coordination is confirmed by single crystal structure determinations of Pt(dppe)(mnt) (1a) and Pt(dppb)(mnt) (3a). Pink crystals of Pt(dppe)(mnt) (1a) (C30H24N2P2PtS2) are monoclinic, space group P21/n (No. 14), with a = 11.491(4) ?, b = 12.484(2) ?, c = 19.822(7) ?, β = 91.34(1)°, V = 2842.90 ?3, Z = 4, and final R = 0.029 (Rw = 0.031) for 4793 unique reflections. Orange crystals of Pt(dppb)(mnt) (3a) (C34H24N2P2PtS2) are monoclinic, space group P21/n (No. 14), with a = 10.050(7) ?, b = 19.301(3) ? c, = 15.800(6) ?, β = 94.36(6)°, V = 3056.28 ?3, Z = 4, and final R = 0.030 (Rw = 0.036) for 5576 unique reflections. The average Pt-S (2.299(7) ? for 1a and 2.301(2) ? for 3a) and Pt-P (2.257(2) ? for 1a and 2.256(7) ? for 3a) bond distances in each structure agree well with previously reported structural results. The metrical parameters of the mnt chelate ring indicate some degree of metal-ligand delocalization in both structures. The 31P NMR spectra of the phosphines resonances for all of the complexes show platinum satellites (1JPt-P = 1100-2500 Hz). In addition, the ecda complexes exhibit complex second-order coupling patterns, arising from the asymmetry of the ecda ligand. All of the complexes exhibit strong emission in the solid state and in frozen glasses at 77 K. Emission spectra are structured for the mnt complexes and broad and featureless for the ecda complexes. Solid-state emission lifetimes at 77 K are in the microsecond range.
