Thiosemicarbazone derivatives of nickel and copper: the unprecedented coordination of furan ring in octahedral nickel(ii) and of triphenylphosphine in three-coordinate copper(i) complexes†
Abstract
The influence of substituents at the C2carbon of N1-substituted thiosemicarbazones, {C4H3X–C2(CH3)N3–N2H–C1(
S)N1HR2} (X = O, S) on the geometry of nickel(II) complexes has been investigated. The presence of a
N3–N2H–C1(
S)N1HR2, R2 = CH3, HaftscN–Me; C2H5, HaftscN–Et; C6H5, HaftscN–Ph} induces unusual coordination by the furan ring and yielded high spin octahedral nickel(II) complexes, [Ni(κ3-O, N3, S-aftscN–R2)2], CH31, C2H52, and 2[Ni((κ3-O, N3, S-aftscN–Ph)2] 3 (μeff = 2.98, 1; 2.96, 2; 2.92, 3). With 2-acetylthiophene-N1-substituted thiosemicarbazones, {(C4H3S)-C2(CH3)
N3-N2H–C1(
S)N1HR2, R2 = CH3, HattscN–Me; C2H5, HattscN–Et; C6H5, HattscN–Ph}, N3, S chelated low spin trans square planar complexes, {[Ni(κ3-O, N3, S-attscN–R2)2], R2 = CH3, 4; C2H5, 5; C6H5, 6} with pendant thiophene rings have been obtained. The bigger sized sulfur atoms of the thiophene rings form short intramolecular contacts with the deprotonated hydrazinic