Lanthanide−Transition-Metal Carbonyl Complexes:  New [Co₄(CO)₁₁]^2-Clusters and Lanthanide(II) Isocarbonyl Polymeric Arrays

Abstract

Two types of Ln(II)-Co(4) isocarbonyl polymeric arrays, [(Et(2)O)(3)(-)(x)()(THF)(x)()Ln[Co(4)(CO)(11)]]( infinity ) (1-3; x = 0, 1) and [(THF)(5)Eu[Co(4)(CO)(11)]]( infinity ) (4), were prepared and structurally characterized. Transmetalation involving Ln(0) and Hg[Co(CO)(4)](2) in Et(2)O yields [(Et(2)O)(3)Ln[Co(4)(CO)(11)]]( infinity ) (1, Ln = Yb; 2, Ln = Eu). Dissolution of the solvent-separated ion pairs [Ln(THF)(x)()][Co(CO)(4)](2) (Ln = Yb, x = 6; Ln = Eu) in Et(2)O affords [(Et(2)O)(2)(THF)Yb[Co(4)(CO)(11)]]( infinity ) (3) and [(THF)(5)Eu[Co(4)(CO)(11)]]( infinity ) (4). In these reactions, oxidation and condensation of the [Co(CO)(4)](-) anions result in formation of the new tetrahedral cluster [Co(4)(CO)(11)](2)(-). The two types of Ln(II)-Co(4) compounds contain different isomers of [Co(4)(CO)(11)](2)(-), and, consequently, the structures of the infinite isocarbonyl networks are distinct. The cluster in [(Et(2)O)(3)(-)(x)()(THF)(x)()Ln[Co(4)(CO)(11)]]( infinity ) (1-3) possesses pseudo C(3)(v)() symmetry (an apical Co, three basal Co atoms; one face-bridging, three edge-bridging, seven terminal carbonyls) and connects to Ln(II) centers through eta(2),micro(4)- and eta(2),micro(3)-carbonyls to generate a 2-D puckered sheet. In contrast, [(THF)(5)Eu[Co(4)(CO)(11)]]( infinity ) (4) incorporates a C(2)(v)() symmetric cluster (two unique Co environments; two face-bridging, one edge-bridging, eight terminal carbonyls), and isocarbonyl linkages (eta(2),micro(4)-carbonyls) to Eu(II) atoms create a 1-D zigzag chain. Complexes 1-4 contain the first reported eta(2),micro(4)-CO bridges between a Ln and a transition-metal carbonyl cluster. Infrared spectroscopic studies revealed that the isocarbonyl associations to Ln(II) persist in solution. The solution structure and dynamic behavior of the [Co(4)(CO)(11)](2)(-) cluster in 1 was investigated by variable-temperature (59)Co and (13)C NMR spectroscopies.

Infinite Molecular {[Pt3n(CO)6n]2–}∞ Conductor Wires by Self‐Assembly of [Pt3n(CO)6n]2– (n = 5–8) Cluster Dianions Formally Resembling CO‐Sheathed Three‐Platinum Cables

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Miscellaneous tetrasubstituted ammonium salts of [Pt 3n -(CO) 6n ]2-(n = 5-8) clusters, obtained by the stoichiometric oxidation of the corresponding [Pt 9 (CO) 18 ] 2-salts with tropylium tetrafluoroborate, self-assemble into infinite semicontinuous or continuous {[Pt 3n (CO) 3n (µ-CO) 3n ] 2-} ϱ conductor wiresOne dimensional molecular metal wires [1,2] and one-and two-dimensional superclusters that are assembled through M-M bonds [3,4] are interesting as low-dimensional molecular materials, and they may find applications in molecular electronics and nanolithography. [5][6][7] According to EHMO calculations, the LUMO of a Pt 3 (CO) 3 (µ-CO) 3 triangular moiety involves the combination of cyclopropenyl-like inphase Pt p z atomic orbitals.

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Synthesis and Crystal Structure of [NBu4]2[Pt24(CO)48]: An Infinite 1D Stack of {Pt3(CO)6} Units Morphologically Resembling a CO‐Insulated Platinum Cable

“…[1,2] To date only discrete [Pt 3n (CO) 6n ] 2À oligomers with n = 1-5 have been selectively synthesized and characterized. [2][3][4][5][6][7] 1D molecular metal wires, [8,9] and 1D and 2D superclusters [10,11] are interesting in themselves as low-dimensional molecular materials with possible applications in molecular electronics and nanolithography. [12][13][14] The recent improvement of the synthesis of "platinum carbonyl" [7] prompted a reinvestigation of the chemistry of the [Pt 3n (CO) (CO) 48 ] reveals a distribution of oligomers centered at n = 5, with peaks of lesser intensity at n = 4 and n = 6.…”

Synthesis, crystal structure and properties of a new lanthanide‐transition metal carbonyl cluster

“…[5 -9] Research has been focused on the elucidation of the interaction between the two metals, and little is known concerning the application of these compounds as catalytic and magnetic materials, although it was suggested that complexes containing Ln-M carbonyls offer the possibility of functioning as catalyst precursors [10 -13] . Until now, the determination of the structural relationship between the two metals has revealed three possible structure types of Ln-M complexes: [14] ion pairs (I), isocarbonyl linkages (II) and Ln-M direct bonds (III), for example, [Ln 9 (OH) 10 (acac) 16 ][HCr 2 (CO) 10 ] (Ln = Sm, Eu, Gd, Dy, Yb) (I), [15] [Yb(THF) 6 ][Co(CO) 4 ] 2 (I), [16] [(THF) 4 I 2 Sm(µ-OC)Mo(CO) 2 (C 5 H 5 )] (II), [17] [(Pry) 4 Yb{(µ-OC) 2 − Co(CO) 2 } 2 ] ∞ (II), [14] {[(CH 3 CN) 3 YbFe(CO) 4 ] 2 CH 3 CN} ∞ (III) [18] and [(NH 3 ) 3 YbFe(CO) 4 ] (III). [19] However, these assorted Ln-M interactions influence the assembly of the compounds, the distance between lanthanide and transition metal is not easy to control and discrete molecules or polymeric arrays were encountered.…”

“…[19] However, these assorted Ln-M interactions influence the assembly of the compounds, the distance between lanthanide and transition metal is not easy to control and discrete molecules or polymeric arrays were encountered. [14] In light of their potential applications and their diverse structural motifs, we are interested in synthesizing a new type of heterobimetallic carbonyl compounds, which contains organic functional groups as bridging ligands. The carbonyl cluster fragment we have chosen is the well-known capped tricobalt (CO) 9 Co 3 C, which is both a versatile electronic donor and acceptor, [20] while the functional group we have chosen is [-COO] − , which has the ability to coordinate to Ln(III) cores.…”