The reaction of bis(3,5-dimethylpyrazol-1-yl)methane (bdmpzm) with Bu
nLi and carbodiimide derivatives, namely,
N,
N'-diisopropyl, dicyclohexyl, and 1-
tert-butyl-3-ethyl carbodiimides, enables the preparation of new heteroscorpionateligands in the form of the lithium derivatives [Li(NNN)(THF)] (NNN = pbpamd (
1) (pbpamd =
N,
N'-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate); cbpamd (
2) (cbpamd =
N,
N'-dicyclohexylbis(3,5-dimethylpyrazol-1-yl)acetamidinate); and tbpamd (
3) (tbpamd =
N-ethyl-
N'-
tert-butylbis(3,5-dimethylpyrazol-1-yl)acetamidinate)), althougha similar process with
N,
N'-dimethylcarbodiimide gave the dinuclear complex [Li(bpzii)(THF)]
2 (
4) (bpzii =
N-(dimethylamino)-
N'-[(dimethylamino)bis(3,5-dimethylpyrazol-1-yl)methylimino]imino). When this last reaction wascarried out in an air atmosphere, the cluster complex [Li
8(
4-O)
2(
4-OH)
2(
4-pz)
2(
2-bpziLi)
2(bpzCN)
2(THF)
4] (
5)(bpziLi = dimethylaminobis(3,5-dimethylpyrazol-1-yl)methyliminolithium, bpzCN = bis(3,5-dimethylpyrazol-1-yl)acetonitrile) was isolated and characterized by X-ray analysis. Finally, when the same process was carried out inthe presence of water the amidine-scorpionate (bpzan) (
6) (bpzan =
N,
N-dimethylbis(3,5-dimethylpyrazol-1-yl)acetamidine) was obtained. Compounds
1 and
3 reacted with [TiCl
4(THF)
2] or [ZrCl
4] to give complexes ofstoichiometry [MCl
3((
3-NNN))] (M = Ti, Zr) (
7-
10). The structures of the different compounds were determined byspectroscopic methods and, in addition, the X-ray crystal structures of
1,
3,
4,
5, and
6 were also established.