| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1306981 | Inorganica Chimica Acta | 2014 | 9 Pages |
•Thiocarboxylate complexes of Ni(II) were prepared and characterized structurally.•Thiocarboxylate group binds monodentately (through S) in [Ni(dppe)(SCOPh)2].•In [Ni(en)(SCOPh)2], [Ni(opda)(SCOPh)2] and [Ni2(SCOPh)4] both O and S are bonded.•The Ni–Ni distance in [Ni2(SCOPh)4·solv] is suggestive of a bond between the two.•Magnetic susceptibility and DFT studies reveal the nature of Ni–Ni bond.
Thiobenzoate complexes of Ni(II), [Ni(dppe)(SCOPh)2] (1), [Ni(en)(SCOPh)2] (2), [Ni(opda)(SCOPh)2] (3), [Ni2(SCOPh)4·EtOH] (4) [Ni2(SCOPh)4·CH3CN] (5) [where dppe = bis(diphenylphosphino)ethane; en = ethylenediamine; opda = orthophenylenediamine] were synthesized and characterized structurally by X-ray crystallography. Electronic absorption spectra were recorded for all the complexes and the same has been computed using time dependent density functional theory for a representative compound (1). Bonding between Ni–Ni atoms in the dimeric unit has been confirmed in 4 and 5 on the basis of X-ray structural analyses and magnetic moment measurements. NBO calculations have been carried out to understand the nature of bonding.
Graphical abstractMono and dinuclear thiobenzoate complexes of Ni(II) have been synthesized and characterized. Existence of Ni–Ni bonds have been confirmed in dinuclear complexes on the basis of X-ray structural analysis and magnetic moment measurements. NBO calculations have been carried out to understand the nature of bonding. The figure shows the dz2–dz2dz2–dz2 orbital overlap of two nickel atoms in the complex 4 and 5. The bond distances obtained by the X-ray diffraction of crystals 4 and 5 fall in the range of Ni–Ni covalent bond distance.Figure optionsDownload full-size imageDownload as PowerPoint slide
