Triphenyl-phosphine and -arsine derivatives of nitratopentacarbonylmaganese(I)

Abstract

Reactions of triphenyl-phosphine (PPh₃) and -arsine (AsPh₃) with nitratopentacarbonylmaganese(I) yield the products Mn(CO)₄PPh₃NO₃, Mn(CO)₄AsPh₃NO₃, and cis- and trans-Mn(CO)₃(PPh₃)₂NO₃. The monosubstituted complexes in the solid state, and the trans-disubstituted complexe, exhibit unusual nitrate infrared absorptions, which may possibly be explained in terms of a pyramidal nitrate group bonding through the nitrogen atom. Structural changes of Mn(CO)₄LNO₃ complexes in CHCl₃ have been followed by infrared spectroscopy. When 2,2′-bipyridyl displaces PPh₃ in trans-Mn(CO)₃(PPh₃)₂NO₃, the bonding of the nitrate group reverts to the unidentate type.