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Methylidene Rare‐Earth‐Metal Complex Mediated Transformations of CN, NN and NH Bonds: New Routes to Imido Rare‐Earth‐Metal Clusters
Author(s) -
Hong Jianquan,
Zhang Lixin,
Wang Kai,
Zhang Yin,
Weng Linhong,
Zhou Xigeng
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201300440
Subject(s) - chemistry , metal , rare earth , carboxylate , thiophenol , reactivity (psychology) , yield (engineering) , acetylene , stereochemistry , crystallography , medicinal chemistry , materials science , organic chemistry , mineralogy , medicine , alternative medicine , pathology , metallurgy
Three new patterns of reactivity of rare‐earth metal methylidene complexes have been established and thus have resulted in access to a wide variety of imido rare‐earth metal complexes [L 3 Ln 3 (μ 2 ‐Me) 3 (μ 3 ‐Me)(μ ‐ NR)] (L=[PhC(NC 6 H 3 i Pr 2 ‐2,6) 2 ] − ; R=Ph, Ln=Y ( 2 a ), Lu ( 2 b ); R=2,6‐Me 2 C 6 H 3 , Ln=Y ( 3 a ), Lu ( 3 b ); R= p ‐ClC 6 H 4 , Ln=Y ( 4 a ), Lu ( 4 b ); R= p ‐MeOC 6 H 4 , Ln=Y ( 5 a ), Lu ( 5 b ); R=Me 2 CHCH 2 CH 2 , Ln=Y ( 6 a ), Lu ( 6 b )) and [{L 3 Lu 3 (μ 2 ‐Me) 3 (μ 3 ‐Me)} 2 (μ ‐ NR′N)] (R′=(CH 2 ) 6 ( 7 b ), (C 6 H 4 ) 2 ( 8 b )). Complex 2 b was treated with an excess of CO 2 to give the corresponding carboxylate complex [L 3 Lu 3 (μ‐η 1 :η 1 ‐O 2 CCH 3 ) 3 (μ‐η 1 :η 2 ‐O 2 C‐CH 3 )(μ‐η 1 :η 1 :η 2 ‐O 2 CNPh)] ( 9 b ) easily. Complex 2 a could undergo the selective μ 3 ‐Me abstraction reaction with phenyl acetylene to give the mixed imido/alkynide complex [L 3 Y 3 (μ 2 ‐Me) 3 (μ 3 ‐η 1 :η 1 :η 3 ‐NPh)(μ 3 ‐CCPh)] ( 10 a ) in high yield. Treatment of 2 with one equivalent of thiophenol gave the selective μ 3 ‐methyl‐abstracted products [L 3 Ln 3 (μ 2 ‐Me) 3 (μ 3 ‐η 1 :η 1 :η 3 ‐NPh)(μ 3 ‐SPh)] (Ln=Y ( 11 a ); Lu ( 11 b ). All new complexes have been characterized by elemental analysis, NMR spectroscopy, and most of the structures confirmed by X‐ray diffraction.