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Eine neuartige Assoziation zwischen Kalium und komplex gebundenem DistickstofF -Struktur von KN 2 Co(PMe 3 ) 3 /A Novel Association of Potassium and Co-ordinated Dinitrogen - Crystal Structure of KN 2 Co(PMe 3 ) 3

1978; De Gruyter; Volume: 33; Issue: 11 Linguagem: Inglês

10.1515/znb-1978-1114

1865-7117

Hans‐Friedrich Klein, Reinhard Hammer, J. Wenninger, Péter Friedrich, Gottfried Hüttner,

Inorganic Chemistry and Materials

Abstract [(Me 3 P) 3 CoN 2 ] 2 Mg(THF) 4 reacts with potassium metal to give [KN 2 Co(PMe 3 ) 3 ] 6 . The same compound is obtained via substitution of olefin in cobaltates K+[Co(olefin)(PMe 3 ) 3 ] - by molecular nitrogen under ambient conditions. Infrared data show that association is preserved even in ether solvents. The stability of cobaltates [Co(PMe 3 ) 3 L] - increases in the order L = olefin < dinitrogen < PMe 3 . Reactions of the title compound proceed as oxidative additions to the monomer with loss of molecular nitrogen. Methyl iodide and allyl bromide yield the fluxional complexes CoCH 3 (PMe 3 ) 4 and η3-C 3 H 5 Co(PMe 3 ) 3 , respectively. Ethyl bromide gives cis-CoH(C 2 H 4 )(PMe 3 ) 3 via β-elimination and coordination of ethylene. The molecular structure of [KN 2 Co(PMe 3 ) 3 ] 6 reveals a novel type of cluster: a double cube made up from six KN 2 units with six exo-Co(PMe 3 ) 3 groups (d(NN) = 116-118 pm, d(CoN) = 170-171 pm).