Heterobimetallic An–Mo (An = U, Th) paddlewheel complexes featuring dative Mo → An bonds are reported.

Separate reactions of [Th{N(CH2CH2NSiMe2But)2(CH2CH2NSi(Me)(But)(-CH2)]2 (1) with [Re(5-C5H5)2(H)] (2) or [Ru(5-C5H5)(H)(CO)2] (3) produced, by alkane elimination, [Th(TrenDMBS)Re(5-C5H5)2] (ThRe, TrenDMBS = {N(CH2CH2NSiMe2But)3}3-), and [Th(TrenDMBS)Ru(5-C5H5)(CO)2] (ThRu), which were isolated in crystalline yields of 71 and 62%, respectively. Complex ThRe is the first example of a molecular Th-Re bond to be structurally characterised, and ThRu is only the second example of a structurally authenticated Th-Ru bond. By comparison to isostructural U-analogues, quantum chemical calculations, which are validated by IR and Raman spectroscopic data, suggest that the Th-Re and Th-Ru bonds reported here are more ionic than the corresponding U-Re and U-Ru bonds.

Uranium-Halide and-Azide Derivatives of the Sterically Demanding TriamidoamineLigand Tren TPS [Tren TPS = {N(CH 2 CH 2 NSiPh 3) 3 } 3-]. Polyhedron.

The D4h isomer of [(OC)5W–W(CO)5]2− is a gas-phase transition state that becomes a true minimum in the solid state.