Tripeldecker‐Komplexe, VIII. Elektrophile Aufstockungsreaktionen von Borataferrocen‐ und Bis(borol)cobaltat‐Ionen mit Tricarbonylmetall‐Fragmenten der Chrom‐ und Mangan‐Gruppe

Abstract

Tripledecker Complexes, VIII. — Electrophilic Stacking Reactions of Borataferrocene and Bis(borole)cobaltate Ions with Tricarbonylmetal Fragments of Chromium and Manganese Group MetalsBis(borole)cobaltate ions [CoL2]‐ (1‐) and borataferrocene ions [CpFeL]‐ (2‐) (a: L = C4H4BMe; b: L = C4H4BPh) readily undergo stacking reactions. When treated with sources of chromium group M(CO)3 fragments, 1b‐ and 2b‐ form 30‐e tripledecked anions [μ‐L(CoL){M(CO)3}]‐ (M = Cr, Mo, W) (3‐ ‐ 5‐) and [μ‐L(FeCp){M(CO)3}]‐ (M = Cr, Mo, W) (6‐‐8‐). These 30‐e anions are very sensitive to nucleophilic degradation by e.g. water, acetonitrile and to a lesser extent acetone. Cyclic voltammetry reveals a reversible oxidation of 6‐ to give the 29‐e neutral tripledecker complex μ‐ L(FeCp)[Cr(CO)3] (6), while the oxidation of the higher homologues is fully irreversible. Protonation of 6‐ ‐8‐ affords hydrido complexes μ‐L(FeCp)[MH(CO)3] (M = Cr, Mo, W) (9–11), and, with PhCH2Br, the benzyl derivate μ‐L(FeCp)‐[W(CO)3(CH2Ph)] (12) is produced. Similar stacking reactions with manganese group M(CO)3 fragments produce neutral tripledecked complexes as e.g. μ‐L(CoL)[Re(CO)3] (14) (L = C4H4BPh). In the case of the reaction of [CpFeL]‐ (2‐) with [Mn(CO)3(NCMe)3]3]PF6 symmetric tripledecker compounds μ‐L[Mn(CO)3]2 (15a,b) and μ‐L(FeCp)2 (16a,b) are formed in a novel dismutation reaction (a: L = C4H4BMe; b: L = C4H4BPh).