The reaction of bis(3,5-dimethy
lpyrazo
l-1-y
l)methane (bdmpzm) with Bu
nLi and carbodiimide derivatives, name
ly,
N,
N'-diisopropy
l, dicyc
lohexy
l, and 1-
tert-buty
l-3-ethy
l carbodiimides, enab
les the preparation of new heteroscorpionate
ligands in the form of the
lithium derivatives [Li(NNN)(THF)] (NNN = pbpamd (
1) (pbpamd =
N,
N'-diisopropy
lbis(3,5-dimethy
lpyrazo
l-1-y
l)acetamidinate); cbpamd (
2) (cbpamd =
N,
N'-dicyc
lohexy
lbis(3,5-dimethy
lpyrazo
l-1-y
l)acetamidinate); and tbpamd (
3) (tbpamd =
N-ethy
l-
N'-
tert-buty
lbis(3,5-dimethy
lpyrazo
l-1-y
l)acetamidinate)), a
lthougha simi
lar process with
N,
N'-dimethy
lcarbodiimide gave the dinuc
lear comp
lex [Li(bpzii)(THF)]
2 (
4) (bpzii =
N-(dimethy
lamino)-
N'-[(dimethy
lamino)bis(3,5-dimethy
lpyrazo
l-1-y
l)methy
limino]imino). When this
last reaction wascarried out in an air atmosphere, the c
luster comp
lex [Li
8(
4-O)
2(
4-OH)
2(
4-pz)
2(
2-bpziLi)
2(bpzCN)
2(THF)
4] (
5)(bpziLi = dimethy
laminobis(3,5-dimethy
lpyrazo
l-1-y
l)methy
limino
lithium, bpzCN = bis(3,5-dimethy
lpyrazo
l-1-y
l)acetonitri
le) was iso
lated and characterized by X-ray ana
lysis. Fina
lly, when the same process was carried out inthe presence of water the amidine-scorpionate (bpzan) (
6) (bpzan =
N,
N-dimethy
lbis(3,5-dimethy
lpyrazo
l-1-y
l)acetamidine) was obtained. Compounds
1 and
3 reacted with [TiC
l4(THF)
2] or [ZrC
l4] to give comp
lexes ofstoichiometry [MC
l3((
3-NNN))] (M = Ti, Zr) (
7-
10). The structures of the different compounds were determined byspectroscopic methods and, in addition, the X-ray crysta
l structures of
1,
3,
4,
5, and
6 were a
lso estab
lished.