Übergangsmetall‐Stannyl‐Komplexe, 9 [1] . Substitutions‐Reaktionen der anionischen Hydrid‐Komplexe [(π‐MeC 5 H 4 )(CO) 2 MnH] – und [(π‐Aromat)(CO) 2 CrH] –

Transition Metal Stannyl Complexes, 9 [1] . – Substitution Reactions of the Anionic Hydrido Complexes [(π‐MeC 5 H 4 )‐(CO) 2 MnH] – and [(π‐Arene)(CO) 2 CrH] – The anionic hydrido complexes K[(π‐MeC 5 H 4 )(CO) 2 MnH] ( 2c ) and K[(π‐arene)(CO) 2 CrH] (π‐arene = C 6 H 6 , C 6 H 5 Me, 1,2,3‐C 6 H 3 Me 3 , C 6 Me 6 , C 6 H 5 Ph, indan) ( 5a–f ) are spontaneously formed on stirring THF solutions of the dianionic complexes K 2 [(π‐MeC 5 H 4 )(CO) 2 Mn] ( 1 ) or K 2 [(π‐arene)(CO) 2 Cr] ( 4 ) at – 78°C. The dianionic complexes are obtained by potassium naphthalenide reduction of (π‐MeC 5 H 4 )(CO) 2 MnL or (π‐arene)(CO) 2 CrL (L = pyridine or THF). Reaction of 2c with Me 3 SnCl or Ph 2 SnCl 2 yields the bis(stannyl) complexes Cp*(CO) 2 Mn(SnR 3 ) 2 (SnR 3 = SnMe 3 , SnPh 2 Cl), while reactions with the „smaller” stannanes Me 2 SnCl 2 or Et 2 SnCl 2 results in the SnR 2 ‐bridged complexes [Cp′(CO) 2 Mn] 2 (μ‐SnR 2 )((M n –M n ). The bis(stannyl) complexes (π‐arene)(CO) 2 Cr(SnR 2 Cl) 2 (R = Me, Ph) are obtained from 5 and R 2 SnCl 2 . However, the reaction is strongly influenced by steric effects: with Me 2 SnCl 2 , bis(stannyl) complexes are obtained for π‐arene = C 6 H 6 , C 6 H 5 Me, 1,2,3‐C 6 H 3 Me 3 , or C 6 Me 6 , with Ph 2 SnCl 2 only for π‐arene = C 6 H 6 and C 6 H 5 Me. Reaction of the sterically demanding complexes K[(π‐C 6 H 5 Ph)(CO) 2 CrH] or K[(π‐indan)(CO) 2 CrH] with Ph 2 SnCl 2 stops at the stage of the anionic stannyl complexes K[(π‐arene)(CO) 2 Cr‐SnPh 2 Cl].