DARSTELLUNG UND EIGENSCHAFTEN VON UND REAKTIONEN MIT METALLHALTIGEN HETEROCYCLEN LV. REDUKTION VON SEKUNDAEREN PHOSPHANKOMPLEXEN DES MANGANS MIT K-SELEKTRID; EIN NEUER WEG ZU PHOSPHAMANGANACYCLOPROPANEN

Article abstract of DOI:10.1016/0022-328X(87)83022-X

The anions K<(OC)4MnPR2H> (2a-e) (R2 = Me2 (a), MePh (b), Ph2 (c), (cyclo-C6H11)2 (d), (t-Bu)2 (e)) are obtained by reaction of (OC)4BrMnPR2H (1a-e) with K.Proton abstraction with BuLi affords the highly nucleophilic phosphidomanganates KLi<(OC)4MnPr2> (3a-e) which exist as contact ionic pairs with Mn-M (M = K, Li) interaction.The action of BuLi on 2a-e proceeds via the formation of contact ionic pairs without Mn-M interaction or the solvent separated ionic pairs 3a^*-c^*, which cannot be separated from each other.When 2a-e is treated with CH2Cl2 in the presence of excess K, the three-membered heterocycles (OC)4MnCH2PR2 (4a-e) with an ylidic bonding system are formed in good yields.In principle 4a-e also result from 3a-e and CH2Cl2 as in demonstrated in the case of 3c -> 4c.