282731-74-2Relevant academic research and scientific papers
Platinum dithiolene complexes of π-coordinating and π-interacting η4-cyclobutadiene ligands
Nomura, Mitsushiro,Fujii, Takashi,Kajitani, Masatsugu
, p. 3776 - 3784 (2009)
Five new organometallic platinum dithiolene complexes of the η4-cyclobutadiene ligand [(η4-C4Me 4)Pt(dithiolene)] (dithiolene = mnt (2), dcmedt (3), tdt (4), dddt (5), dmit (6)) and one platinum diselenolene complex, [(η4-C 4Me4)Pt(dsit)] (7), were prepared from [(η4-C4Me4)Pt(Cl)(w-Cl)]2 (1) and Na2(mnt), O=C(dcmedt), H2tdt, O=C(dddt), (NBu 4)2[Zn(dmit)2], or (NEt4) 2[Zn(dsit)2], respectively. The (η4-C 4Me4)Pt complexes 2-7 were characterized by NMR, UV-vis spectra, and CV. Those 1H and 13C NMR spectra showed 195Pt satellite coupling at the C4Me4 (J pt-H = 13-15 Hz), at the C4Me4 (J Pt-c = ca. 100 Hz), and at the dithiolene carbons. The complexes having an electron-rich dichalcogenolene ligand (5-7) resulted in lower energy electronic absorption compared with the electron-poor series 2-4. The η4-C4Me4 ligand was replaced by the nucleophilic substitution of bis(diphenylphosphino)ethane (DPPE) to form the square-planar [Pt(dithiolene)(dppe)] complex. 2, 3, and 5-7 were structurally determined by X-ray diffraction studies. All the molecules were monomeric, had two-legged piano-stool geometries, and were formal 16-electron complexes with the PtII (d8) center. The crystal structure of 2 showed an inversion-centered dyad. 5 had η4-C4Me4- ... -dithiolene plane-to-plane interaction in the crystal to form a zigzag chain. 6 and 7 were isostructural to each other and had intermolecular interactions through η4-C4Me4- ... -trithiocarbonate contacts to form a zigzag chain. The η4-C 4Me4 group behaves as a π-coordinating ligand and a π-interacting ligand as well. Dithiolene and diselenolene ligands used in this work were as follows: mnt = maleonitrile-1,2-dithiolate, dcmedt = 1,2-dimethoxycarbonylethylene-1,2-dithiolate, tdt = toluene-3,4-dithiolate, dddt = 5,6-dihydrol,4-dithiine-2,3-dithiolate, dmit = 1,3-dithiol-2-thione-4,5- dithiolate, and dsit = 1,3-dithiol-2-thione-4,5diselenolate.
Reaction of the tetrachalcogenides [ME4(dppe)] (M = Pd, E = S; M = Pt, E = S, Se) with activated alkynes to form dithiolenes and diselenolenes
Ford, Susan,Lewtas, Mark R.,Morley, Christopher P.,Di Vaira, Massimo
, p. 933 - 938 (2007/10/03)
The tetrachalcogenides [ME4(dppe)] (M = Pd, E = S; M = Pt, E = S, Se) react with the activated alkynes RO2CC≡CCO2R (R = Me, Et) to form the dithiolenes and diselenolenes [M{E2C2(CO2R)2
