Organometallic nickel(II) complexes containing thiolate and dithiocarbamate ligands

The mono(pentafluorophenyl) nickel(II) complexes [Ni(C6F5)CIL2] (L = PPhMe2 , PPh2Me; L-2 = dppe) react with KSR (R = Ph, C6H4Me-p, C6H4OMe-p, C6H4Cl-p , C6H3Cl2- 2,6, C6H4NO2-p) at room temperature in acetone/dichloromethane t o give the mononuclear thiolate complexes [Ni(C6F5)(SR)L-2]. The binuclear mu-thiolate complex [{Ni(C6F5)(PPhMe2)}(2)(mu-SC6H4NO2-P)(2)] is Obtained b y reaction of KSC6H4NO2-p with the same chloro complex in refluxing dichlor omethane. A single-crystal X-ray diffraction study of [Ni(C6F5) (SC6H4NO2-P ) (PPhMe2)(2)] and [Ni-2(C6F5)(2)(PPhMe2)(2)(mu-SC6H4NO2-P)(2)] has establi shed the mononuclear and binuclear nature of the complexes. The dithiocarba matenickel complexes [Ni(C6F5)(S2CNR2)L] (L = PPhMe2, PPh2Me, PEt3; R = Et, iPr; R-2 = C5H10, C4H8O) have been prepared by reaction of [Ni(C6F5)CIL2] (L = PPhMe2, PPh2Me, PEt3) with the alkali metal salt of the corresponding dithioacid, A single-crystal X-ray diffraction study of [Ni(C6F5)(S2CNiPr2) (PPhMe2)] has established the mononuclear nature of the complex, and the ge ometry around each Ni atom as that of a tetrahedrally distorted square-plan ar geometry. Analytical (C, H, N), spectroscopic (IR, H-1, and F-19 NMR), E md mass spectrometry (FAB) data have been used for structural assignments.