The reaction of bis(3,5-di
methy
lpyrazo
l-1-y
l)
methane (bd
mpz
m) with Bu
nLi and carbodii
mide derivatives, na
me
ly,
N,
N'-diisopropy
l, dicyc
lohexy
l, and 1-
tert-buty
l-3-ethy
l carbodii
mides, enab
les the preparation of new heteroscorpionate
ligands in the for
m of the
lithiu
m derivatives [Li(NNN)(THF)] (NNN = pbpa
md (
1) (pbpa
md =
N,
N'-diisopropy
lbis(3,5-di
methy
lpyrazo
l-1-y
l)aceta
midinate); cbpa
md (
2) (cbpa
md =
N,
N'-dicyc
lohexy
lbis(3,5-di
methy
lpyrazo
l-1-y
l)aceta
midinate); and tbpa
md (
3) (tbpa
md =
N-ethy
l-
N'-
tert-buty
lbis(3,5-di
methy
lpyrazo
l-1-y
l)aceta
midinate)), a
lthougha si
mi
lar process with
N,
N'-di
methy
lcarbodii
mide gave the dinuc
lear co
mp
lex [Li(bpzii)(THF)]
2 (
4) (bpzii =
N-(di
methy
la
mino)-
N'-[(di
methy
la
mino)bis(3,5-di
methy
lpyrazo
l-1-y
l)
methy
li
mino]i
mino). When this
last reaction wascarried out in an air at
mosphere, the c
luster co
mp
lex [Li
8(
![](/i<font color=)
mages/entities/
mgr.gif">
4-O)
2(
![](/i<font color=)
mages/entities/
mgr.gif">
4-OH)
2(
![](/i<font color=)
mages/entities/
mgr.gif">
4-pz)
2(
![](/i<font color=)
mages/gifchars/kappa.gif" BORDER=0 >
2-bpziLi)
2(bpzCN)
2(THF)
4] (
5)(bpziLi = di
methy
la
minobis(3,5-di
methy
lpyrazo
l-1-y
l)
methy
li
mino
lithiu
m, bpzCN = bis(3,5-di
methy
lpyrazo
l-1-y
l)acetonitri
le) was iso
lated and characterized by X-ray ana
lysis. Fina
lly, when the sa
me process was carried out inthe presence of water the a
midine-scorpionate (bpzan) (
6) (bpzan =
N,
N-di
methy
lbis(3,5-di
methy
lpyrazo
l-1-y
l)aceta
midine) was obtained. Co
mpounds
1 and
3 reacted with [TiC
l4(THF)
2] or [ZrC
l4] to give co
mp
lexes ofstoichio
metry [MC
l3((
![](/i<font color=)
mages/gifchars/kappa.gif" BORDER=0 >
3-NNN))] (M = Ti, Zr) (
7-
10). The structures of the different co
mpounds were deter
mined byspectroscopic
methods and, in addition, the X-ray crysta
l structures of
1,
3,
4,
5, and
6 were a
lso estab
lished.