Spin Crossover in Novel Dihydrobis(1-pyrazolyl)borate [H(2)B(pz)(2)]-Containing Iron(II) Complexes. Synthesis, X-ray Structure, and Magnetic Properties of [FeL{H(2)B(pz)(2)}(2)] (L = 1,10-Phenanthroline and 2,2'-Bipyridine).

Abstract

The first example of spin crossover iron(II) complexes based on dihydrobis(1-pyrazolyl)borate are presented here. The complexes {Fe[H(2)B(Pz)(2)](2)(phen)} (phen = 1,10-phenanthroline), 1, and {Fe[H(2)B(Pz)(2)](2)(bipy)} (bipy = 2,2'-bipyridine), 2, have been synthesized and their structures determined by X-ray diffraction methods. Crystals 1 and 2 are monoclinic, space group C2/c, Z = 4 with a = 17.448(4) Å, b = 16.101(4) Å, c = 10.611(2) Å, and beta = 112.47(2) degrees for 1 and a = 16.307(2) Å, b = 15.075(4) Å, c = 11.024(4) Å, and beta = 114.95(5) degrees for 2 at 293 K. The crystal structure of 2 was also determined at 139 K in order to detect the structural changes associated with the S = 0 <--> S = 2 spin conversion. 2 retains the same space group upon spin conversion with a = 16.086(6) Å, b = 14.855(6) Å, c = 10.812(2) Å, and beta = 114.18(3) degrees. The structures of 1 and 2 are made up of mononuclear neutral species where the positive charge of iron(II) is neutralized through the coordination of two chelate bidentate dihydrobis(pyrazolyl)borate anions, and phen or bipy neutral ligands are used to fill the iron(II) coordination sphere. The molecular structures for both compounds are very similar, with Fe-N bond lengths in the 2.212-2.158 Å range for the high-spin phase. The structural modifications associated with the spin change in 2 mainly consist of a large reorganization of the metal environment: the Fe-N decreases by 0.15 Å (mean value) when the temperature is lowered from 290 to 139 K and a more regular shape of the [FeN(6)] octahedron is achieved through a slight modification of the trigonal deformation angle from 5.3 degrees to 3.2 degrees along with remarkable variations of the N-Fe-N angles. The thermodynamic model of Slichter and Drickamer was applied to account for the magnetic data. The intermolecular interaction parameter and the enthapy and entropy changes associated with the spin transition were estimated as Gamma = 3.3 kJ mol(-)(1), DeltaH = 13.4 kJ mol(-)(1), and DeltaS = 81.9 J mol(-)(1) K(-)(1) for 1 and Gamma = 1.7 kJ mol(-)(1), DeltaH = 13.4 kJ mol(-)(1), and DeltaS = 83.9 J mol(-)(1) K(-)(1) for 2, respectively.