Synthese und Struktur von Schwefel‐, Schwefelmonoxid‐ und Schwefeldioxid‐ verbrückten dimetallischen Komplexen des Typs [M(CO)(dppm)] 2 (μ‐S)(μ‐L) und [(CO) 3 M'(dppm) 2 MX](μ‐L') (M = Rh, Ir; M' = Mo, W, Mn; L = SO, SO 2 ; L' = S, SO 2 ; X = Cl, CO)

Synthesis and Structure of Sulfur‐, Sulfur Monoxide‐, and Sulfur Dioxide‐Bridged Dimetallic Complexes of the Type [M(CO)(dppm)] 2 (μ‐S)(μ‐L) and [(CO) 3 M'(dppm) 2 MX](μ‐L') (M = Rh, Ir; M' = Mo, W, Mn; L = SO, SO 2 ; L' = S, SO 2 ; X = Cl, CO) The homo‐ and heterodimetallic complexes [M(CO)(dppm)] 2 ‐(μ‐S)(μ‐SO 2 ) (M = Rh, Ir) ( 2a, b ), [(CO) 3 M'(dppm) 2 MCl](μ‐SO 2 ) (M' = Mo, W; M = Rh, Ir) ( 4a – c ), and [(CO) 3 Mn(dppm) 2 ‐ Rh(CO)] ( 6 ) by passing sulfur dioxide through their solutions. The X‐ray structure analysis of 5a shows the SO 2 ligand in a bridging position, whereas one CO ligand is semibridging. Treatment of the same starting materials with thiirane S ‐oxide does not lead to the corresponding SO‐bridged dimers, with the only exception of 1b , which yields the new SO complex [(Ir(CO)(dppm)] 2 (μ‐S)(μ‐SO) ( 3b ). Passing H 2 S through a solution of 6 , the sulfur‐bridged complex [(CO) 3 Mn(dppm) 2‐ Rh(CO)](μ‐S) ( 8 ) is formed, accompanied by H 2 elimination.