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Dalton Transactions

The international journal for inorganic, organometallic and bioinorganic chemistry



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Dalton Trans., 2010, 39, 221 - 226, DOI: 10.1039/b918181d

Isocyanate diinsertion into the N–H bond of the 2-pyridylamino ligand of organolanthanides

Yan Sun, Zhengxing Zhang, Xu Wang, Xiaoqing Li, Linhong Weng and Xigeng Zhou

[Cp2LnNHPy]2 (Py = 2-pyridyl) ( 1a–e) react with phenyl isocyanate to form the N–H diinsertion products Cp2Ln[2:1-PyNCON(Ph)CONHPh](THF) (Ln = Yb ( 3a), Er ( 3b), Y ( 3c), Dy ( 3d), Gd ( 3e)). It has been proven that nPr2NH can abstract one PhNCO unit from 3c to form Cp2Y[3-OC(NHPh)NPy] ( 2c) and nPr2NHCONHPh ( 4), representing a rare example of selective release of a functional group of ligands in organolanthanide chemistry. Hydrolysis of 2c gives the organic nitrogen-containing product PyNHCONHPh ( 5). Moreover, 3c can also be obtained by the reaction of 2c with PhNCO. These results demonstrate that the diinsertion of PhNCO into the N–H bond of coordinated amino ligands might proceed in a stepwise manner. All the compounds were characterized by elemental analysis and spectroscopic properties. The structures of compounds 3a–e and 4 are also determined through X-ray single-crystal diffraction analysis.

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