Thioureato-verbrückte zweikernige Komplexe der Lanthanoide Darstellung und Struktur von [{PhC(NPh)NC(S)NEt2}{Et2NC(S)NH}LnBr(thf)]2 (Ln = Gd,Sm)

Thioureato Brigded Binuclear Complexes of the Lanthanides Synthesis and Crystal Structure of [{PhC(NPh)NC(S)NEt₂}{Et₂NC(S)NH}LnBr(thf)]₂ (Ln = Gd, Sm) The reaction of potassium-N-(diethylaminothiocarbonyl)-N′-phenyl-benzamidinat with LnBr₃ (Ln = Gd, Sm) leads to the formation of the binuclear complexes [{PhC(NPh)NC(S)NEt₂}{Et₂NC(S)N}LnBr(thf)]₂} (Ln = Gd 1 , Sm 2 ). The two bridging thiureatoligands are probably built during the reaction of potassium with the starting ligand. Coordination by one N-(diethylaminothiocarbonyl)-N′-phenylbenzamidinato-ligand, one Br-ion and one THF-ligand leads to square antiprismatic coordination of the lanthanoids. The structures of both compounds were characterized by X-ray analysis ( 1 : P1 (Nr.2), Z = 1, a = 12,006(4) Å, b = 12,245(4) Å, c = 13,612(3) Å, α = 70,55(3)°, β = 68,21(3)°, γ = 81,31(3)° 2 : P1 (Nr.2), Z = 1, a = 11,803(3) Å, b = 12,344(5) Å, c = 12,797(8) Å, α = 103,07(5)°, β = 101,76(3)°, γ = 114,13(3)°)     

Synthese und Struktur eines Molybdän–Gadolinium-Heterometall-Komplexes Die Struktur von [Li(thf)4]2[Cp2MoSGdBr4(thf)]2

Synthesis and structure of a Molybdenum–Gadolinium Heterometallic Complex. The Structure of [Li(thf)₄]₂[Cp₂MoSGdBr₄(thf)]₂ [Cp₂MoHLi] reacts in THF with S and GdBr₃ to yield the tetranuclear heterobimetallic complex [Li(thf)₄]₂[Cp₂MoSGdBr₄(thf)]₂. The bonding situation and the structure of this compound were characterized by X-ray structure analysis (space group P1 (No. 2), Z = 1, a = 10.845(2) Å, b = 12.166(2) Å, c = 15.881(2) Å, α = 101.74(2)°, β = 97.62(2)°, γ = 103.97(2)°). Each S atom of the central Mo₂S₂-ring is coordinated by a GdBr₄(thf) fragment. Additionally each Mo atom is connected to two Cp ligands. This leads to a tetrahedral coordination of the Mo atoms and a octahedral coordination of the Gd ions.     

Neue Komplexe der Lanthanoiden mit zweizähnigen Liganden. Die Strukturen von [(C17H17N2)GdBr2(thf)2] und [(C17H17N2)3Ln] (L = Sm,Gd)

New Complexes of the Lanthanoides with Bidentate Ligands. The Crystal Structures of [(C₁₇H₁₇N₂)GdBr₂(thf)₂] and [(C₁₇H₁₇N₂)₃Ln] (L = Sm, Gd) Reaction of [(AIP)Li] with GdBr₃ leads to a new mononuclear complex [(AIP)GdBr₂(thf)₂] 1 . In contrast to this with SmI₂ the compound [(AIP)₃Sm] 2 is build up. Such complexes are also formed with Gd(OR^*)₃ (R^* = O^tBu₂C₆H₃) and [(AIP)Li] in a 1:3 ratio, [(AIP)₃Gd] 3 . The structures of 1–3 were characterized by X-ray single crystal structure analysis ( 1 : space group Pna2₁ (No. 33), Z = 4, a = 1 972.7(9) pm, b = 984.7(5) pm, c = 1 425.0(8) pm, α = β = γ = 90°; 2 · 2 THF: space group C2/c (No. 15), Z = 8, a = 3 644.4(9) pm, b = 1 437.5(5) pm, c = 2 334.4(7) pm, β = 1 21.07(6)°; 3 : space group P2(1)/c (No. 14), Z = 4, a = 1 872.9(1) pm, b = 1 064.6(1) pm, c = 2 282.4(2) pm, β = 103.75(8)°).     

Neue Benzylkomplexe der Lanthanoiden. Darstellung und Kristallstrukturen von [(C5Me5)2Y(CH2C6H5)(thf)], [(C5Me5)2Sm(CH2C6H5)2K(thf)2]∞ und [(C5Me5)Gd(CH2C6H5)2(thf)]

New Benzyl Complexes of the Lanthanides. Synthesis and Crystal Structures of [(C₅Me₅)₂Y(CH₂C₆H₅)(thf)], [(C₅Me₅)₂Sm(CH₂C₆H₅)₂K(thf)₂]_∞, and [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] YBr₃ reacts with potassium benzyl and [K(C₅Me₅)] in THF to give KBr and the monobenzyl compound [(C₅Me₅)₂ · Y(CH₂C₆H₅)(thf)] 1 . The analogous reaction with SmBr₃ in THF leads to the polymeric product [(C₅Me₅)₂Sm(CH₂C₆H₅)₂ ∞ K(thf)₂]_∞ 2 , with GdBr₃ to [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] 3 . The structures of 1–3 were determined by X-ray single crystal structure analysis:

• Space group P1 , Z = 2, a = 851.2(4) pm, b = 952.7(4) pm, c = 1858.6(8) pm, α = 79.90(4)°, β = 77.35(4)°, γ = 73.30(3)°.
• Space group P1 , Z = 2, a = 903.3(2) pm, b = 1375.9(3) pm, c = 1801.1(4) pm, α = 100.92(3)°, β = 100.77°, γ = 98.25(3)°.
• Space group P2₁/n, Z = 8, a = 1458.2(5) pm, b = 927.8(3) pm, c = 3792.9(15) pm, β = 96.83(3)°.

     

Zur Reaktion der Lanthanoiden mit Chelatliganden Darstellung und Struktur von [(py2CH)3Gd]

On the Reaction of the Lanthanides with Chelate Ligands Synthesis and Crystal Structure of [(py₂CH)₃Gd] GdBr₃ reacts with [(py₂CH)Li] to the mononuclear complex [(py₂CH)₃Gd] 1 . The structure of 1 was characterized by X-ray single crystal structure analysis. Space group P2₁, Z = 2, a = 951.4(10) pm, b = 1369.4(10) pm, c = 1074.5(10) pm, β = 105.69(8)°. The Gd-Ion is surrounded by the six nitrogen atoms of the three chelate ligands and shows a distorted trigonal prismatic coordination. As a difference to the lithium salt of the ligand, the six-membered metalla-cycles in 1 are not planar, but show a boat conformation.