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Ligand‐ Substrate Communication in Group 4 Aminopyridinato Complexes
Author(s) -
Oberthür Markus,
Hillebrand Gerhard,
Arndt Perdita,
Kempe Rhett
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971300618
Subject(s) - chemistry , agostic interaction , ligand (biochemistry) , trimethylsilyl , moiety , zirconium , stereochemistry , medicinal chemistry , substrate (aquarium) , metal , crystal structure , crystallography , inorganic chemistry , organic chemistry , receptor , geology , biochemistry , oceanography
Tris(aminopyridinato) zirconium and ansa‐aminopyridinato titanium complexes have been sythesized. The reaction of (TMS‐APy) 3 ‐Zr‐Cl (4‐methyl‐2‐trimethylsilyl‐aminopyridine=TMS‐APy‐H) with trimethylsilylbutadiynyl lithium generated in situ affords (TMS‐APy) 3 ZrCCCCTMS ( 1 ). (TMS‐apy) 3 ‐Zr‐Me 2 ( 2 ). Compound 2 shows an agostic interaction of the dimethylamido moiety. The reaction of Ti(NMe, 2 ), 4 with silox(Apy‐H) 2 1,3‐di(4′‐picolin‐2′‐yl‐amino)‐1,1,3,3‐tetraisopropyldisiloxane=silox (APy‐H) 2 ] gives rise to silox(Apy) 2 ‐Ti‐(NMe 2 ) 2 ‐Ti‐[NMe, 2 ) 2 ( 3 ). Complex 3 reacts with ε‐caprolactam to form a caprolactamato complex ( 4 ). X‐ray crystal structure analyses of 1, 2, 3 and 4 are reported. The complexes 1, 2, 3 and 4 may be considered to be strained donor‐functionalized amido(metal) complexes due to the η 2 binding mode of the ligand cores,TMS‐APy and silox(APy) 2 , to meet the requirements of the ancillary coordinated substrates is observed. Thus, aminopyridinato complexes seem to be valuable model compounds for investigations of ligand‐substrate communications in early transition metal chemistry.