Synthesis and Structural Characterization of 2,6-Dimesitylphenyl Complexes of Scandium, Ytterbium, and Yttrium

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• 作者：Gerd W. Rabe ; Christian D. B&eacute ; rub&eacute ; Glenn P. A. Yap ; Kin-Chung Lam ; Thomas E. Concolino ; and Arnold L. Rheingold
• 刊名：Inorganic Chemistry
• 出版年：2002
• 出版时间：March 25, 2002
• 年：2002
• 卷：41
• 期：6
• 页码：1446 - 1453
• 全文大小：99K
• 年卷期：v.41,no.6(March 25, 2002)
• ISSN：1520-510X

文摘

The molecular structures of a number of 2,6-dimesitylphenyl-based (2,6-dimesitylphenyl = Dmp) complexes of thegroup 3 elements scandium and yttrium as well as of the lanthanide element ytterbium are reported. Reaction of1 equiv of DmpLi with 1 equiv of MCl₃ (M = Sc, Yb, Y) in tetrahydrofuran at room temperature followed bycrystallization from toluene/hexanes at -30 es/entities/deg.gif">C produces DmpMCl₂(THF)₂ (M = Sc: 1; M = Yb: 2) and DmpMCl₂(THF)₃ (M = Y: 3), respectively. The one-pot reaction of DmpLi with 1 equiv of YbCl₃ in tetrahydrofuran at roomtemperature followed by addition of 1 equiv of KO^tBu produces the heterobimetallic monoalkoxide complex DmpYb(THF)(O^tBu)(es/entities/mgr.gif">-Cl)₂Li(THF)₂ (4), which was crystallized from toluene/tetrahydrofuran (20:1) at -30 es/entities/deg.gif">C. Crystal datafor 1: monoclinic, P2₁/n; T = 203 K; a = 10.178(3) Å; b = 15.468(3) Å; c = 20.132(5) Å; es/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 101.85(3)es/entities/deg.gif">; V =3102.0(17) ų; Z' = 4; D_calcd = 1.228 g cm^-3; R₁ = 5.89%. Crystal data for 2: monoclinic, P2₁/n; T = 173 K; a= 10.2447(7) Å; b = 15.5683(12) Å; c = 20.0979(14) Å; es/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 101.749(4)es/entities/deg.gif">; V = 3238.3(5) ų; Z' = 4; D_calcd =1.485 g cm^-3; R₁ = 4.32%. Crystal data for 3: monoclinic, P2₁/n; T = 203 K; a = 15.950(3) Å; b = 11.865(2)Å; c = 18.254(3) Å; es/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 92.323(3)es/entities/deg.gif">; V = 3451.9(10) ų; Z' = 4; D_calcd = 1.327 g cm^-3; R₁ = 4.43%. Crystal datafor 4: triclinic, Pes/entities/onemacr.gif">; T = 193 K; a = 10.2252(2) Å; b = 11.3497(2) Å; c = 18.5814(2) Å; es/gifchars/alpha.gif" BORDER=0> = 98.7353(6)es/entities/deg.gif">; es/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> =102.8964(6)es/entities/deg.gif">; es/gifchars/gamma.gif" BORDER=0 > = 94.8058(5)es/entities/deg.gif">; V = 2062.09(5) ų; Z' = 2; D_calcd = 1.375 g cm^-3; R₁ = 4.56%. The molecularstructures of 1-3 feature monomeric complexes with distorted trigonal-bipyramidal (1 and 2) or octahedral (3)coordination geometry about the metal atom, with the two chlorine atoms occupying the axial positions. 4 representsthe first example of an alkoxide derivative of a terphenyl lanthanide complex. The molecular structure of the atecomplex 4 exhibits a heavily distorted trigonal-bipyramidal coordination polyhedron about the ytterbium atom, withone of the es/entities/mgr.gif">-chlorine atoms and the oxygen atom of the tetrahydrofuran ligand representing the axial positions ofthe trigonal-bipyramidal arrangement. A terminal alkoxide ligand is another main feature of the molecular structureof complex 4.