Lanthanide–Transition Metal Carbonyl Complexes: Condensation of Solvent-Separated Ion-Pair Compounds into Extended Structures.

New solvent-separated ion-pair compounds and extended structures containing ytterbium(II)-transition metal isocarbonyl linkages were synthesized. [Yb(THF)8][M(CO)5]2 (1, M = Mn; 2, M = Re) were prepared via transmetalation reactions between Yb metal and Hg[M(CO)5]2 in THF. Reflux of 1 in Et2O afforded {Yb(THF)2-(Et2O)2[(μ-CO)2Mn(CO)3]2}∞ (3) which is a sheet-layer structure. In ether solution, 3 is converted to {Yb(THF)4-[(μ-CO)2Mn(CO)3]2}∞ (4) which has a linear structure. In both 3 and 4, ytterbium is 8-coordinated (distorted square antiprism geometry), four coordination sites occupied by molecules of solvent and four more by oxygen atoms of isocarbonyl linkages. The [Mn(CO)5]- anion has trigonal bipyramidal geometry and is linked to ytterbium through two equatorial carbonyls. The formation of two minor products, (THF)2Mn3(CO)10 (5) and [(THF)5Yb(μ-CO)Mn3-(CO)13][Mn3(CO)14] (6), was observed during condensation of 1 into 3 and 4. [ABSTRACT FROM AUTHOR]