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

Tripledecker Complexes, VIII. — Electrophilic Stacking Reactions of Borataferrocene and Bis(borole)cobaltate Ions with Tricarbonylmetal Fragments of Chromium and Manganese Group Metals Bis(borole)cobaltate ions [CoL 2 ] ‐ ( 1 ‐ ) and borataferrocene ions [CpFeL] ‐ ( 2 ‐ ) ( a : L = C 4 H 4 BMe; b : L = C 4 H 4 BPh) 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 PhCH 2 Br, the benzyl derivate μ‐L(FeCp)‐[W(CO) 3 (CH 2 Ph)] ( 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 = C 4 H 4 BPh). In the case of the reaction of [CpFeL] ‐ ( 2 ‐ ) with [Mn(CO) 3 (NCMe) 3 ] 3 ]PF 6 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 = C 4 H 4 BMe; b: L = C 4 H 4 BPh).