139042-49-2Relevant academic research and scientific papers
Synthesis and Structures of (Monoorganyl)amides and -imides of Zirconium and Hafnium
Bai, Yueniu,Roesky, Herbert W.,Noltemeyer, Mathias,Witt, Michael
, p. 825 - 832 (2007/10/02)
The tetrahalides MCl4 (M = Zr 1a, Hf 1b) react with LiNHtBu with elimination of LiCl to yield 2 (3) (M = Zr 3a, Hf 3b).Compounds 3 are thermally instable and oligomerise above 100 deg C with elimination of H2NtBu.The reactions of (η5-C5Me5)MCl3 (M = Zr 1c, Hf 1d) with LiNHR (R = tBu 2a, 2,4,6-Me3C6H2 2b, 2,6-iPr2C6H3 2c) lead to (η5-C5Me5)M(NHR)3 (4) (R = t-Bu, M = Zr 4a, Hf 4b; R = 2,4,6-Me3C6H2, M = Zr 4c, Hf 4d; R = 2,6-iPr2C6H3, M = zr 4e, Hf 4f).Compounds 4 are thermally very stable and melt without decomposition.When 1c and 1d react with LiNHPh (2d), dimers of composition 5-C5Me5)2M(NHPh)NPh>2 (M = Zr 5a, Hf 5b) are obtained.The complexes (η5-C5Me5)2M(NHR)2 (6) (M = Zr 6a, Hf 6b).Pyridine reacts with 4e at 85 deg C and replaces one molecule of 2,6-iPr2C6H3NH2 to give (η5-C5Me5)Zr(NHR)NR*Py (7).The single crystal X-ray structures of 4a, 4f, 5b and 7 are described. Key Words: Zirconium amides, imides / Hafnium amides, imides / Amides / Imides / ZrN double bond
