Three gallyl lanthanide complexes [{(dipp-Bian)Ga} 2 Ln(thf) 4 ] (Ln = Sm, Eu, Yb; dipp-Bian = 1,2-bis[(2,6diisopropylphenyl)imino]acenaphthene), in which the lanthanide atoms are coordinated by only two {(dipp-Bian)Ga} − ligands and THF, are reported. Two unsupported Ln−Ga bonds are found in each compound. The gallyl lanthanide complexes have been obtained by two synthetic pathways: (1) reductive insertion of the lanthanide metals into the Ga−Ga bond of [{(dipp-Bian)Ga}] 2 and (2) salt metathesis of [(dipp-Bian)GaK(thf) 5 ] with LnI 2 . Moreover, the samarium compound [{(dipp-Bian)Ga} 2 Sm(thf) 4 ] was additionally obtained in a reductive pathway from SmI 3 and [(dipp-Bian)GaK(thf) 5 ]. The length of the Ln−Ga bond strongly depends on packing effects. The reaction of TmI 2 (thf) 5 and [(dipp-Bian)GaK(thf) 5 ] gave the Tm(III) complex [{(dipp-Bian)Ga−Ga(dipp-Bian)}(C 4 H 8 O)TmI(thf) 5 ], in which one THF ring was opened and reduced twice, forming the formal double negative charged anion (O-CH 2 -CH 2 -CH 2 -CH 2 ) 2− . This thulium compound and its dysprosium analogue [{(dipp-Bian)Ga−Ga(dipp-Bian)}(C 4 H 8 O)DyI(thf) 5 ] were also obtained in an alternative approach by reacting LnI 2 (thf) x (Ln = Tm, Dy) with [(dipp-Bian)Ga] 2 in THF. All new compounds were structurally characterized by single-crystal X-ray diffraction. The ytterbium complex shows the shortest Yb(II)−Ga bond distances reported so far.

Octanuclear lanthanide–iron clusters: The first lanthanide–carbonyl–sulfide–iron clusters were obtained by redox reactions of [(η5‐C5Me5)2Ln(thf)2] (Ln=Sm, Yb) and [Fe2(μ‐S2)(CO)6]. The resulting wheel‐shaped clusters have 14‐membered peripheral rings with [Fe6(μ3‐S)6(CO)12]2− units in the center (see picture).