The coordination behavior, the conformational flexibility, and the stability of the novel (pyrazol-1-yl)borate ligands [Ph(pz)B(mu-N(Me))(mu-pz)B(pz)Ph](-) ([L-1](-)), [Ph(pz)B(mu-O)(mu-pz)B(pz)Ph](-) ([L-2](-)), and [Ph(pz)B(mu-O)(mu-OB(Ph)O)B(pz)Ph](2-) ([L-3](2-)) have been experimentally assessed by investigating the following compounds: [Li(thf)L-1], [Li(thf)L-2], [Mg(Cl)(thf)(x)L-1], [Mg(Cl)(thf)(2)L-2], [Mn(CO)(3)L-2], K(thf[Mn(CO)(3)L-3], [CoCl2(HL1)], [(LCo)-Co-1(mu-Cl)(2)CoL1], [Zn(Br)L-1], [Cu(Cl)L-1], [Cu(Cl)L-2]. The L-1-complexes were prepared from a mixture of HL1 and the appropriate metal salt by addition of a base. HCl elimination from [CoCl2(HL1)], which gives [(LCo)-Co-1(mu-Cl)(2)CoL1], does not necessarily require the assistance of a base, but happens spontaneously when a solution of the complex is stored at room temperature for several days. K(thf)[Mn(CO)(3)L-3] was obtained via in situ hydrolysis of HL1/[Mn(CO)(5)Br] in the presence of K2CO3. In some other cases, formation of the coordination compounds proceeded with decomposition of a part of the ligand molecules and yielded pyrazole (e.g., [Zn(Cl)(Hpz)L-2]) or pyrazolide (e.g., [(LCo)-Co-2(mu-Cl)(mu-pz)CoL2]) complexes. As evidenced by the crystal structure analyses of [Zn(Br)L-1]/[Mg(Cl)(thf)(2)L-2]/[Mn(CO)(3)L-2] on the one hand and [(LMg)-Mg-1(mu-Cl)(2)Mg(thf)L-1]/[Cu(Cl)L-1/[Cu(Cl)L-2](2) on the other, [L-1](-) and [L-2](-) are able to adopt both a facial and a meridional conformation. Moreover, while many of the established design principles of scorpionate chemistry are still valid for [L-1](-), [L-2](-), and [L-3](2-), the bonding situation of the central donor moiety (N(Me) in [L-1](-); O in [L-2](-), [L-3](2-)) is distinctly different from the way the pyrazolyl rings are attached to the molecule, so that donor scrambling is not an issue in these [N,N,N] and [N,O,N] mixed-donor ligands.