1,6‐Heptadien‐Nickel(0)‐Komplexe: rac/meso‐(μ‐η2,η2‐C7{Ni( η2,η2‐C7H12)}2 und L‐Ni(η2,η2‐C7H12)

1,6‐Heptadiene Nickel(0) Complexes:rac/meso‐(μ‐η2,η2‐C7{Ni(η 2,η2‐C7H12)}2 und L‐Ni(η2,η2‐C7H12) Ni(CDT) dissolves in 1,6‐heptadiene with displacement of the CDT to yield the dinuclear homoleptic product rac/meso‐(μ‐ η2,η2‐C7H12){Ni(η2, η2‐C7H12)}2 (1) as a mixture of stereoisomers, in which the nic...

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Veröffentlicht in:Chemische Berichte 1991-12, Vol.124 (12), p.2667-2675
Hauptverfasser: Proft, Bernd, Pörschke, Klaus‐Richard, Lutz, Frank, Krüger, Carl
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Sprache:eng
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Zusammenfassung:1,6‐Heptadiene Nickel(0) Complexes:rac/meso‐(μ‐η2,η2‐C7{Ni(η 2,η2‐C7H12)}2 und L‐Ni(η2,η2‐C7H12) Ni(CDT) dissolves in 1,6‐heptadiene with displacement of the CDT to yield the dinuclear homoleptic product rac/meso‐(μ‐ η2,η2‐C7H12){Ni(η2, η2‐C7H12)}2 (1) as a mixture of stereoisomers, in which the nickel atoms are trigonal‐planar coordinated by a chelating 1,6‐diene ligand and one CC bond of a bridging diene ligand. The stereoisomers differ in the coordination mode of the bridging diene ligand.‐The bridging diene ligand in 1 can be displaced by various donor/acceptor molecules. In pentane, 1 reacts with ethene to yield a solution of mononuclear (C2H4)Ni(η2,η2‐C7H12) (2). With alkynes unstable complexes are formed of which the anticipated ethyne derivative (C2H2)Ni(η2,η2‐C7H12) (3) decomposes explosively at – 100°C. With isocyanides, methylenephosphoranes, methyllithium, amines, pyridines, phosphanes, and phosphites (i.e. C, N, P donors) crystalline complexes of type L‐Ni(η2.η2 C7H12) have been obtained, of which the derivatives with L=tBuN  C 4, Me3PCH2 5, LiCH3 6, C7H13N7, C5H5N 8, Me3P 9, iPr3P 10, Ph3P 11, (PhO)3P 12 are characterized here. For 11 the crystal structure has been determined.
ISSN:0009-2940
1099-0682
DOI:10.1002/cber.19911241206