Synthesis and Structure of Novel Cu‐Clusters: [Cu 30−x Se 15 (P i Pr 3 ) 12 ] (x = 0,1) and [Cu 36 Se 18 (P t Bu 3 ) 12 ]

In contrast to the system phosphane/AgCl , the system phosphane/CuCl reacts with Se(SiMe 3 ) 2 below 20°C to give metal‐rich cluster complexes in yields of 60%. Above 100°C, binary copper selenides are formed. Compounds 1 – 3 were characterized by X‐ray structure analysis. They are the largest Cu cluster compounds so far known. The structures of 1 and 2 reveal a cluster framework whose polyhedral surfaces are covered with μ 4 ‐Se, μ 5 ‐Se, and μ 6 ‐Se ligands.