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)6][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.