Osmium−Alkenylcarbyne and −Alkenylcarbene Complexes with an Steroid Skeleton: Formation of a Testosterone Organometallic Derivative Containing the 7H-Amino Adenine Tautomer

Complex OsH2Cl2(PiPr3)2 (1) reacts with ethisterone to give the hydride−alkenylcarbyne complex OsHCl2(CCHC19H26O)(PiPr3)2 (2) containing the testosterone skeleton. Treatment of 2 with AgBF4 in the presence of acetonitrile leads to [OsH(CCHC19H26O)(CH3CN)2(PiPr3)2](BF4)2 (3), which evolves into the alkenylcarbene derivative [Os(CHCHC19H26O)(CH3CN)3(PiPr3)2](BF4)2 (4). The reaction of 2 with TlPF6 in a dichloromethane:acetone mixture affords [OsHCl(CCHC19H26O)(κ1-OCMe2)(PiPr3)2]PF6 (5), which coordinates adenine to give [OsHCl(CCHC19H26O)(7H-amino-adenine)(PiPr3)2]PF6 (6) containing, in addition to the androgen, a 7H-amine-adenine tautomer. The X-ray diffraction structures of 2 and 6 are also reported.