The chiral, enantiopure bis(pyrazol-1-yl)methane-based NNO-donor scorpionate ligands in the form of the alcohol compounds bpzbeH (bpzbe = 1,1-bis(3,5-dimethylpyrazol-1-yl)-3,3-dimethyl-2-butoxide), bpzteH (bpzte = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-p-tolylethoxide), and (R,R)-bpzmmH ((R,R)-bpzmm = (1R)-1-{(1R)-6,6-dimethylbicyclo[3.1.1]-2-hepten-2-yl}-2,2-bis(3,5-dimethylpyrazol-1-yl)ethoxide) have been used to obtain new NNO-heteroscorpionate yttrium and lutetium complexes. The reactions of bpzbeH, bpzteH (racemic mixtures), and (R,R)-bpzmmH (enantiopure compound) with [M{N(SiHMe2)2}3(thf)2] (M = Y, Lu) in a 1:1 molar ratio in toluene afforded the mononuclear bis(silylamide) complexes [M{N(SiHMe2)2}2(κ3-NNO)(thf)] (M = Y, Lu; 1–6), respectively. When the reaction was carried out with a 2:1 molar ratio (ligand to metal precursor) or with excess ligand, homoleptic complexes of the type [Y(κ3-NNO)2(κ-O-NN)] (κ3-NNO = κ-O-NN = bpzbe (7), bpzte (8)) were obtained. Compounds 1 and 3 were used as convenient st...