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Issue 25, 2010
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Synthesis and exchange reactions of Ni-dimine-COD, acetylene and olefin complexes

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Abstract

The complexes MesDADNi(COD) (1), DippDADNi(COD) (2), DippDABNiCOD (3) and DippBIANNi(COD) (5) were readily prepared from Ni(COD)2. The analogous reaction of the ligand MesBIAN afforded (MesBIAN)2Ni (4). The related Ni alkyne complexes DADNi(PhC[triple bond, length as m-dash]CPh) (6), DippDABNi(PhC[triple bond, length as m-dash]CPh) (7) and DippBIANNi(PhC[triple bond, length as m-dash]CPh) (8) are readily prepared by addition of alkyne to solutions of the COD species. The analogous reactions employing tBuDAD ligand with either Ni(COD)2 alone or Ni(COD)2 and PhC[triple bond, length as m-dash]CPh led only to the known bis-ligand Ni complex, although tBuDADNi(MeCO2C[triple bond, length as m-dash]CCO2Me) (9) is readily prepared. In a similar fashion, the species DippDADNi(MeCO2C[triple bond, length as m-dash]CCO2Me) (10), DippDABNi(Me3SiC[triple bond, length as m-dash]CSiMe3) (11), DippDABNi(MeCO2C[triple bond, length as m-dash]CCO2Me) (12) and DippBIANNi(MeCO2C[triple bond, length as m-dash]CCO2Me) (13) were prepared. Reactions with olefins afforded DippDABNi(MeCO2CH[double bond, length as m-dash]CHCO2Me) (14), DippDABNi(MeCO2CH[double bond, length as m-dash]CHPh) (15). Employing isolated (3) or (15) in exchange reactions afforded (7), (11) (14) and (15). Similarly (6) served as a precursor to (10) while (11) reacts with PhC[triple bond, length as m-dash]CPh to give (7). The solid state structures of (1), (3)–(7), (9), (11) and (15) are reported.

Graphical abstract: Synthesis and exchange reactions of Ni-dimine-COD, acetylene and olefin complexes

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Publication details

The article was received on 21 Jan 2010, accepted on 17 Mar 2010 and first published on 06 Apr 2010


Article type: Paper
DOI: 10.1039/C001312A
Citation: Dalton Trans., 2010,39, 5786-5794

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    Synthesis and exchange reactions of Ni-dimine-COD, acetylene and olefin complexes

    M. J. Sgro and D. W. Stephan, Dalton Trans., 2010, 39, 5786
    DOI: 10.1039/C001312A

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