Third‐Generation Scorpionates [RBpz3]– – How Influential Is the Nondonor Substituent R?

Abstract

Five pairs of perfluorophenyl-and phenyl-substituted tris(pyrazol-1-yl)borate complexes have been prepared and thoroughly investigated, namely, [(C 6 R′ 5 Bpz 3 ) 2 Fe], [(C 6 R′ 5 Bpz 3 ) 2 Cu], [(C 6 R′ 5 Bpz 3 )Mn(CO) 3 ], K[(C 6 R′ 5 Bpz 3 )Mo(CO) 3 ], and [(C 6 R′ 5 Bpz 3 )Mo(CO) 2 (2-methallyl)] (R′ = F, H; pz = pyrazol-1yl). X-ray crystal structure analyses and IR spectroscopical measurements reveal only a minor influence of the spectator substit- [a]

The First Anticancer Tris(pyrazolyl)borate Molybdenum(IV) Complexes: Tested in Vitro and in Vivo—A Comparison of O,O‐, S,O‐, and N,N‐Chelate Effects

“…In compounds 1-6 three non-equivalent resonances for each of the 4-CH,5 -CH pyrazole-ring protons and the iPr CH protons in a 1:1:1r atio were observed in the 1 HNMR spectraa sw ell as six resonances due to the CH 3 groups of the iPr,indicating C 1 sym-metry,a sd escribed in the literature. [29][30][31][32] The Tp iPr ligand was characterized by six methyl group resonanceso ft he iPr at 0.65-1.51 ppm and three CH protons between2 .54-3.96 ppm. The three signals for the 4-CH pyrazole ring protons were found between 5.70-6.55 ppm and the three signals for the 5-CH between 7.23-8.09 ppm, respectively.C ompound 6 bearing a N,N-chelate shows ac onsiderable upfield shift of two of the Tp-methyl group signals, one even into negative ppm values (À0.11, 0.17 ppm), which has been reported previously for other N-donor complexes.…”

C-Homoscorpionate Oxidation Catalysts—Electrochemical and Catalytic Activity

“…It was also found, from electrochemical experiments [57,59], that changes on the functionalized methine group of tris(pyrazol-1-yl) scorpionates have a much smaller influence on the ligand properties than when performed at the pyrazol-1-yl rings (see below).…”

“…Scheme 2. Peroxidative oxidation of cyclohexane to cyclohexanone and cyclohexanol (KA oil) in aqueous medium, catalyzed by C-scorpionate catalysts [7,8,13,43,[46][47][48][49][57][58][59][60][61][62][63][64][65][66][67][68].…”

Spin Crossover in New Iron(II) Coordination Compounds with Tris(pyrazol-1-yl)Methane

“…This review is a logical extension of our paper [20] and is devoted to the latest studies of spin crossover in Fe(II) complexes with tris(pyrazol-1-yl)methane (HC(pz)3) and its derivatives ( Figure 1). We will give a comparative characteristic with bis(B-scorpionate) iron(II) complexes, but we will not touch on the third-fifth generation of scorpionates, which are well described in [21,22]. The steric aspects of ligand design for the control of the metal ion spin state are clear enough.…”