Synthesis, Structural Authentication, and Structurally Defined Metalation Reactions of Lithium and Sodium DA-Zincate Bases (DA = diisopropylamide) with Phenylacetylene
作者:William Clegg、Joaquín García-Álvarez、Pablo García-Álvarez、David V. Graham、Ross W. Harrington、Eva Hevia、Alan R. Kennedy、Robert E. Mulvey、Luca Russo
DOI:10.1021/om8001813
日期:2008.6.9
to trigonal-planar dialkyl-Zn anions via bridging DA ligands. Reaction of 4 and 2 with phenylacetylene affords the bimetallic acetylides [(TMEDA)·Li(C≡CPh)2Zn(tBu)}2·(TMEDA)] (5) and [(TMEDA)·Na(C≡CPh)2Zn(tBu)}2 ] (6), respectively. X-ray crystallographic studies reveal 5 is a pseudodimer (tetranuclear) with two (LiCZnC) rings linked at the Zn atoms by a bridging, nonchelating TMEDA ligand; in contrast
Transamination chemistry of sodium TMP-zincate: synthesis and crystal structure of a chiral amidozincate
作者:David R. Armstrong、William Clegg、Sophie H. Dale、Joaquín García-Álvarez、Ross W. Harrington、Eva Hevia、Gordon W. Honeyman、Alan R. Kennedy、Robert E. Mulvey、Charles T. O'Hara
DOI:10.1039/b713987j
日期:——
In a new type of reactivity for sodium TMP-zincate [(TMEDA)NaZn(tBu)2(TMP)] (1), transamination reactions with the amines diisopropylamine, DA(H), hexamethyldisilazane, HMDS(H) and chiral (R)-N-benzyl-α-methylbenzylamine have produced new sodium amido-di-tert-butyl zincates (all structurally characterised) with concomitant loss of TMP(H).