The reaction of bi
s(3,5-dimethylpyrazol-1-yl)methane (bdmpzm) with Bu
nLi and carbodiimide derivative
s, namely,
N,
N'-dii
sopropyl, dicyclohexyl, and 1-
tert-butyl-3-ethyl carbodiimide
s, enable
s the preparation of new hetero
scorpionateligand
s in the form of the lithium derivative
s [Li(NNN)(THF)] (NNN = pbpamd (
1) (pbpamd =
N,
N'-dii
sopropylbi
s(3,5-dimethylpyrazol-1-yl)acetamidinate); cbpamd (
2) (cbpamd =
N,
N'-dicyclohexylbi
s(3,5-dimethylpyrazol-1-yl)acetamidinate); and tbpamd (
3) (tbpamd =
N-ethyl-
N'-
tert-butylbi
s(3,5-dimethylpyrazol-1-yl)acetamidinate)), althougha
similar proce
ss with
N,
N'-dimethylcarbodiimide gave the dinuclear complex [Li(bpzii)(THF)]
2 (
4) (bpzii =
N-(dimethylamino)-
N'-[(dimethylamino)bi
s(3,5-dimethylpyrazol-1-yl)methylimino]imino). When thi
s la
st reaction wa
scarried out in an air atmo
sphere, the clu
ster complex [Li
8(
![](/image<font color=)
s/entitie
s/mgr.gif">
4-O)
2(
![](/image<font color=)
s/entitie
s/mgr.gif">
4-OH)
2(
![](/image<font color=)
s/entitie
s/mgr.gif">
4-pz)
2(
![](/image<font color=)
s/gifchar
s/kappa.gif" BORDER=0 >
2-bpziLi)
2(bpzCN)
2(THF)
4] (
5)(bpziLi = dimethylaminobi
s(3,5-dimethylpyrazol-1-yl)methyliminolithium, bpzCN = bi
s(3,5-dimethylpyrazol-1-yl)acetonitrile) wa
s i
solated and characterized by X-ray analy
si
s. Finally, when the
same proce
ss wa
s carried out inthe pre
sence of water the amidine-
scorpionate (bpzan) (
6) (bpzan =
N,
N-dimethylbi
s(3,5-dimethylpyrazol-1-yl)acetamidine) wa
s obtained. Compound
s 1 and
3 reacted with [TiCl
4(THF)
2] or [ZrCl
4] to give complexe
s of
stoichiometry [MCl
3((
![](/image<font color=)
s/gifchar
s/kappa.gif" BORDER=0 >
3-NNN))] (M = Ti, Zr) (
7-
10). The
structure
s of the different compound
s were determined by
spectro
scopic method
s and, in addition, the X-ray cry
stal
structure
s of
1,
3,
4,
5, and
6 were al
so e
stabli
shed.