[Cp
2Yb(
o-H
2NC
6H
4S)]
2·2THF (
1) and Cp
2Yb(
p-H
2NC
6H
4S)(THF) (
2) were prepared in goodyields by the protonolysis of Cp
3Yb with the corresponding amino-substituted thiophenol inTHF at room temperature, respectively. Treatment of [Cp
2Yb(
o-H
2NC
6H
4S)]
2·2THF (
1) withPhNCO gives the une
xpected intermolecular addition/cyclization/elimination product [(C
5H
5)
2Yb(
-
1:
3-OSNC
7H
4)]
2 (
3), while Cp
2Yb(
p-H
2NC
6H
4S)(THF) (
2) reacts with PhNCO underthe same conditions to form the simple insertion product {Cp
2Yb[
-
1:
3-OC(
p-H
2NC
6H
4S)NPh]}
2·2THF (
4), demonstrating that the neighboring NH
2 group participation could leadto unique isocyanate insertion reactivity. The structures of all the comple
xes were confirmedby X-ray single-crystal diffraction analysis, indicating that comple
xes
1 and
4 have anunusual intermolecular hydrogen bond interaction involving THF, and a novel intramolecular
-
weak interaction between aromatic rings is also observed in
4.