Binuclear Nickel(II) Complexes Based on Bridging Oxalate and Pseudohalides as Peripheral Ligands: Synthesis, Crystal Structure, DFT Calculations and Magnetic Properties of [{Ni(X)(dien)}2(μ-ox)]·nH2O Complexes (X = N3−, NCS−,n= 0; NCO−,n= 1)

Abstract

Nickel(II) molecular complexes were obtained by water displacement reactions of [{Ni(dien)(H2O)}2(μ‐ox)]Cl2 and the corresponding pseudohalide. The three nickel(II) compounds [{Ni(N3)(dien)}2(μ‐ox)] (1), [{Ni(NCO)(dien)}2(μ‐ox)] · H2O (2) and [{Ni(NCS)(dien)}2(μ‐ox)] (3) are almost isostructural. The structure determinations reveal the presence of a binuclear complex with C2h symmetry, where the oxalate ligand is coordinated in a bis(bidentate) fashion to the twofold related nickel atoms. The distorted octahedral environment of each nickel atom is completed by the three nitrogen atoms of the diethylenetriamine ligand in a fac arrangement and one nitrogen atom from a pseudohalide ligand. Magnetic susceptibility data in the temperature range 4.2−300 K shows intramolecular antiferromagnetic coupling.

A new binuclear Ni(II) complex, an effective A3-coupling catalyst in solvent-free condition

“…In addition, two perchlorate anions play a counter-ion role. The bond distances of oxygens in oxalato ligand and nickel centers are in the range of 2.0809(12) and 2.1005(12) Å (with a mean bond length of 2.0907 Å), which are similar to formerly reported same compound bond lengths [ [12] , [13] , [14] ]. Ni–N bond lengths are from 2.0810(16) to 2.1058(15) Å (with an average bond longitude of 2.0971 Å).…”

“…Oxalate-based dinuclear complexes consist of a wide range of transition metals such as copper [ 3 , 4 ], manganese [ 5 ], zinc [ 6 , 7 ], iron [ 2 ], cobalt [ 8 ], and zirconium [ 9 ]. Among these, several binuclear μ-oxalato Ni(II) complexes were reported previously and their properties were investigated [ [10] , [11] , [12] , [13] , [14] ]. These types of complexes due to the oxalato ligand ability in the establishing the magnetically and structural relationships between complex species have attracted much attention within inorganic chemistry [ 12 , 15 ].…”

Water Displacement by Cyanogold Complexes in Binuclear Nickel(II) Compounds Based on Bridging Oxalate. Synthesis, Structural Diversity, Magnetic Properties, and DFT Calculations

“…Although the MP2 level of theory predicts geometries of gold complexes in good agreement with experiment,21b it is computationally too demanding for systems as large as models 1 − 3 . Hence, density functional theory (B3PW91 22 level of theory), which has been shown to be reliable for studies of open-shell Ni(II) coordination compounds, has been used. To incorporate the mass-velocity and Darwin relativistic terms, the Los Alamos effective core potential combined with a DZ basis (LANL2DZ) 24 was chosen for the transition metals, as a compromise between accuracy and the computational power available.…”

Density functional theory study of the magnetic coupling interaction in a series of binuclear oxalate complexes

“…A significant amount of magnetostructural research work during the past two decades has been devoted to analyzing the remarkable ability of the oxalate bridge to mediate exchange coupling between first-row transition metal ions in both homo-and heteropolynuclear compounds [19][20][21][22]. The most important ability of oxalate ion is the formation of homo-and heterometallic two- [23] and three-dimensional [24] networks that have applications as molecular-based magnetic materials.…”