Photochemical Reaction of Decacarbonyldirhenium with Thiophene and Crystal Structure of Tetradecacarbonylhydridotrirhenium

The photochemical reaction of Re 2 (CO) 10 with thiophene in hexane solution was investigated under vacuum. Three rhenium clusters: H 2 Re 3 (CO) 12 , HRe 3 (CO) 14 and Re 3 (CO) 14 (OH) 4 , were isolated. The structure of Fellmann‐Kaesz cluster Complex HRe 3 (CO) 14 was determined by use of the X‐ray diffraction method. The three rhenium atoms form a plane of symmetry and L: Re 1 Re 2 Re 3 is 107°. The ten carbonyl groups bonded to the two terminal rhenium atoms Re 1 and Re 3 , are staggered with respect to the central rhenium atoms. The bond lengths are 3.10 Å for Re 2 ‐Re 3 and 3.34 Å for Re 1 ‐Re 2 . The bridging hydride is between Re 1 and Re 2 .