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Addition of Nitriles to Alkaline Earth Metal Complexes of 1,2‐Bis[(phenyl)imino]acenaphthenes
Author(s) -
Fedushkin Igor L.,
Morozov Alexander G.,
Rassadin Oleg V.,
Fukin Georgii K.
Publication year - 2005
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.200500330
Subject(s) - chemistry , acenaphthene , protonation , medicinal chemistry , metal , ligand (biochemistry) , alkaline earth metal , reagent , magnesium , nuclear magnetic resonance spectroscopy , amine gas treating , stereochemistry , organic chemistry , naphthalene , ion , biochemistry , receptor
Compounds [Sr(dpp‐bian)(thf) 4 ] ( 2 ), [Ba(dpp‐bian)(dme) 2.5 ] ( 3 ) and [Mg(dtb‐bian)(thf) 2 ] ( 4 ) (dpp‐bian=1,2‐bis[(2,6‐diisopropylphenyl)imino]acenaphthene; dtb‐bian=1,2‐bis[(2,5‐di‐ tert ‐butylphenyl)imino]acenaphthene) were prepared by reduction of dpp‐bian and dtb‐bian with an excess of metallic Mg, Sr, or Ba in THF or DME. Reactions of [Mg(dpp‐bian)(thf) 3 ], 3 , and 4 with diphenylacetonitrile gave keteniminates [Mg(dpp‐bianH)(NCCPh 2 )(thf) 2 ] ( 5 ), [Mg(dtb‐bianH)(NCCPh 2 )(thf) 2 ] ( 6 ), and [Ba(dpp‐bianH)(NCCPh 2 )(dme) 2 ] ( 7 ), respectively. The reaction of 2 with CH 3 CN in THF gave [{Sr(dpp‐bianH)[N(H)C(CH 3 )C(H)CN](thf)} 2 ] ( 8 ). The compounds 2 , 3 , 5 – 8 were characterized by elemental analysis, and IR and NMR spectroscopy. Molecular structures of 2 , 3 , 7 , and 8 were determined by single‐crystal X‐ray diffraction. In contrast to reactions of alkali‐metal reagents, magnesium amides, or yttriumalkyls with α‐H acidic nitriles, which are accompanied by an amine or an alkane elimination, the reactions of [Mg(dpp‐bian)(thf) 3 ] ( 1 ), 2 , 3 , and 4 with such nitriles proceeded with formation of Mg, Sr, and Ba keteniminates and simultaneous protonation of one nitrogen atom of the bian ligand. The NMR spectroscopic data obtained for complex 5 indicated that in solution the amino hydrogen atom underwent the fast (on the NMR timescale) shuttle transfer between both nitrogen atoms of the dpp‐bianH ligand.