Direct Lanthanide−Transition Metal Interactions:  Synthesis of (NH₃)₂YbFe(CO)₄and Crystal Structures of {[(CH₃CN)₃YbFe(CO)₄]₂·CH₃CN}_∞and [(CH₃CN)₃YbFe(CO)₄]_∞

Abstract

The heterometallic complex (NH(3))(2)YbFe(CO)(4) was prepared from the reduction of Fe(3)(CO)(12) by Yb in liquid ammonia. Ammonia was displaced from (NH(3))(2)YbFe(CO)(4) by acetonitrile in acetonitrile solution, and the crystalline compounds {[(CH(3)CN)(3)YbFe(CO)(4))](2).CH(3)CN}(infinity) and [(CH(3)CN)(3)YbFe(CO)(4)](infinity) were obtained. An earlier X-ray study of {[(CH(3)CN)(3)YbFe(CO)(4)](2).CH(3)CN}(infinity) showed that it is a ladder polymer with direct Yb-Fe bonds. In the present study, an X-ray crystal structure analysis also showed that [(CH(3)CN)(3)YbFe(CO)(4)](infinity) is a sheetlike array with direct Yb-Fe bonds. Crystal data for {[(CH(3)CN)(3)YbFe(CO)(4)](2).CH(3)CN}(infinity): monoclinic space group P2(1)/c, a = 21.515(8) Å, b = 7.838(2) Å, c = 19.866(6) Å, beta = 105.47(2) degrees, Z = 4. Crystal data for [(CH(3)CN)(3)YbFe(CO)(4)](infinity): monoclinic space group P2(1)/n, a = 8.364(3) Å, b = 9.605(5) Å, c = 17.240(6) Å, beta = 92.22(3) degrees, Z = 4. Electrical conductivity measurements in acetonitrile show that these acetonitrile complexes are partially dissociated into ionic species. IR and NMR spectra of the solutions reveal the presence of [HFe(CO)(4)](-). However, upon recrystallization, the acetonitrile complexes show no evidence for the presence of [HFe(CO)(4)](-) on the basis of their IR spectra. The solid state MAS (2)H NMR spectra of deuterated acetonitrile complexes give no evidence for [(2)HFe(CO)(4)](-). It appears that rupture of the Yb-Fe bond could occur in solution to generate the ion pair [L(n)Yb](2+)[Fe(CO)(4)](2-), but then the highly basic [Fe(CO)(4)](2-) anion could abstract a proton from a coordinated acetonitrile ligand to form [HFe(CO)(4)](-). However, upon crystallization, the proton could be transferred back to the ligand, which results in the neutral polymeric species.

Lanthanide-Containing Molecular and Supramolecular Polymetallic Functional Assemblies

“…One example is the material An organometallic ladder polymer with direct YbFe bonds has been described by Shore and coworkers. 195 It is produced by reducing Fe 3 (CO) 12 by Yb in liquid ammonia and crystallization at low temperature produces orange polymeric material with formula {[(MeCN) 3 -YbFe(CO) 4 ] 2 ‚xMeCN} (x ) 0, 1). The YbFe(CO) 4 units have a distorted trigonal-bipyramidal geometry around iron, while that of Yb(II) ions is a distorted octahedron.…”

Non-traditional ligands in f-block chemistry

“…Under C 3v symmetry, the d 10 [Fe(CO) 4 ] 2K dianion formally possesses a lone pair directed towards an axial site, which results in the coordination sphere of ytterbium being further supplemented by an Fe/Yb dative donor-acceptor interaction that forms the rungs of the ladders by linking the two strands of the ladder together. Shore (Deng et al 1996) subsequently reported a lattice solvent-free modification of 2, namely [(MeCN) 3 YbFe (CO) 4 ] N (3). The X-ray crystal structure of orange 3 revealed a polymeric sheet network (figure 1b).…”

A Novel Cyanide-Bridged Thulium-Nickel Heterobimetallic Polymeric Complex {(H2O)2(DMF)10Tm2[Ni(CN)4]2}[Ni(CN)4] including O-H…N Hydrogen Bond

“…The cyanide groups of [M(CN) 4 ] 2− (M = transition metal) can be used as bidentate ligands which bridge metal atoms. 5,6 Therefore, our focus has been on synthesizing the lanthanide and transition heterobimetallic complexes containing cyanidebridged ligands. We have investigated the preparation of cyanide-bridged lanthanide and transition heterobimetallic complexes.…”