[{ReN(PMe 2 Ph) 3 }{ReO 3 N}] 2 – Structural Evidence for the Nitridotrioxorhenate(VII) Anion, [ReO 3 N] 2−

Air‐stable, orange‐red single crystals of [{ReN(PMe 2 Ph) 3 }{ReO 3 N}] 2 are formed when mer ‐[ReNCl 2 (PMe 2 Ph) 3 ] reacts with strong bases in MeOH. The resulting centrosymmetric tetranuclear complex contains each two {ReN(PMe 2 Ph) 3 } 2+ and {ReO 3 N} 2− building blocks. They are connected by two oxygen and two nitrogen atoms giving an almost planar {Re 4 O 2 N 2 } ring. The Re–N–Re bridges are only slightly bent (175.2(2)°), while the Re–O–Re angles are 160.9(1)°. The coordination environment of the rhenium atom in the nitridotrioxorhenate(VII) anion is a slightly distorted tetrahedron with O–Re–O and O–Re–N angles between 108.7(1)° and 111.3(1)°.