Photochemical Reaction of Decacarbonyldirhenium with Thiophene and Crystal Structure of Tetradecacarbonylhydridotrirhenium

The photochemical reaction of Re2(CO)10 with thiophene in hexane solution was investigated under vacuum. Three rhenium clusters: H2Re3(CO)12, HRe3(CO)14 and Re3(CO)14(OH)4, were isolated. The structure of Fellmann‐Kaesz cluster Complex HRe3(CO)14 was determined by use of the X‐ray diffraction method. The three rhenium atoms form a plane of symmetry and L: Re1Re2Re3 is 107°. The ten carbonyl groups bonded to the two terminal rhenium atoms Re1 and Re3, are staggered with respect to the central rhenium atoms. The bond lengths are 3.10 Å for Re2‐Re3 and 3.34 Å for Re1‐Re2. The bridging hydride is between Re1 and Re2.