The direct reactions of (C
5H
5)
2LnCl with LiN=C(NMe
2)
2 proceeded at room temperature in THF under pure nitrogento yield the lanthanocene guanidinate complexes [(C
5H
5)
2Ln(
![](/images/entities/mgr.gif)
-
1:
2-N=C(NMe
2)
2)]
2 (Ln = Gd (
1), Er (
2)). Treatmentof phenyl isocyanate with complexes
1 and
2 results in monoinsertion of phenyl isocyanate into the Ln-N(
![](/images/entities/mgr.gif)
-Gua)bond to yield the corresponding insertion products [(C
5H
5)
2Ln(
![](/images/entities/mgr.gif)
-
1:
2-OC(N=C(NMe
2)
2)NPh)]
2 (Ln = Gd (
3), Er(
4)), presenting the first example of unsaturated organic small molecule insertion into the metal-guanidinate ligandbond. Further investigations indicate that
N,
N'-diisopropylcarbodiimide does not react with complexes
1 and
2under the same conditions; however, it readily inserts into the lithium-guanidinate ligand bond of LiN=C(NMe
2)
2.As a synthon of the insertion product Li[(
iPrN)
2C(N=C(NMe
2)
2)], its reaction with (C
5H
5)
2LnCl gives the novelorganolanthanide complexes containing the guanidinoacetamidinate ligand, (C
5H
5)
2Ln[(
iPrN)
2C(N=C(NMe
2)
2)] (Ln= Yb (
5), Er (
6), Dy (
7)). All complexes were characterized by elemental analysis and spectroscopic properties.The structures of complexes
1,
3,
5 and
7 were determined through X-ray single-crystal diffraction analysis.