Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, LII. Bindungs- und Strukturverhältnisse von Phosphidocobaltaten in Lösung und im festen Zustand/ Preparation and Properties of, and Reactions with, Metal-Containing Heterocycles, LII. Bonding and Structural Conditions of Phosphidocobaltates in Solution and in Solid State

Abstract

Abstract Reduction of [(OC)3CoPPh2]n (1a ) with excess sodium granules affords [(OC)3CoPPh2]Na2 (3a) in solution as well as in solid state. However, in analogous reactions of [(OC)3CoPR2H]2 (1b : R = C6H11; 1c : R = t-Bu) with excess sodium granules the monovalent anionic complexes [(OC)3CoPR2H]Na (2b, c) are obtained in THF solution. 2b, c cannot be isolated in solid state. After removal of THF from their solutions the purified residues were identified by elemental analyses as [(OC)3CoPR2]Na2 (3b, c). Addition of buthyllithium to THF solutions of 3a, 2b, c gives rise to differently solvated complexes 3a*-c* which are transformed to [(OC)3CoPR2]M2 (M = N a, Li; 3 a′-c′). The course of the reactions and the products are controlled IR and 31PNMR spectroscopically. 2b, c and 3a, b′, c′ were trapped with (H3CO)2SO2 and CH2X2(X = Cl, I) yielding H3CCo(CO)3PR2H(6b, c), H3CCo(CO)3PR2CH3 (4a - c ) and [xxx] (5a, b), respectively.