Die Deprotonierung silylierter Amido-Komplexe von Seltenerdelementen

Karl, Marc; Harms, Klaus; Seybert, Gert; Massa, Werner; Fau, Stefan; Frenking, Gernot; Dehnicke, Kurt

doi:10.1002/(sici)1521-3749(199912)625:12<2055::aid-zaac2055>3.3.co;2-p

Cited by 16 publications

(22 citation statements)

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“…The bond lengths in the range of d (ScN)=210.7(1)–212.5(1) pm in Li 3 [ScN 2 ] are slightly shorter than the corresponding bond lengths in the binary δ ‐ScN compound with Sc in octahedral coordination ( d (ScN) ≈225 pm). In coordination compounds the ScN bond lengths usually fall in the range of 204–220 pm 26–29. The Li atom is displaced from the center of the nitrogen tetrahedra towards one trigonal face, as indicated by three shorter distances d (LiN)=209.7(6), 210.6(6), and 222.8(6) pm, which are in the range expected for Li in tetrahedral or trigonal planar coordination by N,1–3 and one longer distance d (LiN)=245.6(6) pm.…”

Section: Resultsmentioning

confidence: 98%

Li₃[ScN₂]: The First Nitridoscandate(III)—Tetrahedral Sc Coordination and Unusual MX₂ Framework

Niewa

Zherebtsov

Leoni

2003

Chemistry A European J

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Li(3)[ScN(2)] was prepared from Li(3)N with Sc or ScN in a nitrogen atmosphere at 1020 K as a light yellow powder with an optical band gap of about 2.9 eV. The crystal structure was refined based on X-ray and neutron powder diffraction data (Ia$\bar 3$, Z=16, X-ray diffraction: R(profile)=0.078, R(Bragg)=0.070; Neutron diffraction: R(profile)=0.077, R(Bragg)=0.074; Rietfeld: a=1003.940(8) pm, Guinier: a=1004.50(3) pm). Li(3)[ScN(2)] is an isotype of Li(3)[AlN(2)] and Li(3)[GaN(2)] and crystallizes in an ordered superstructure of the Li(2)O structure type, leading to a three-dimensional framework of all-vertex-sharing tetrahedra 3[infinity[ScN[4/2][3-]]. Li is displaced from the center of a tetrahedron of N atoms in the direction of one trigonal face. Li(3)[ScN(2)] decomposes above 1050 K to form ScN and Li(3)N. Calculations of the periodic nodal surface (PNS) and of the electron localization function (ELF) support the picture of a covalent Sc-N network separated from isolated Li cations, whereby scandium d orbitals are involved in the chemical bonding.

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Section: Resultsmentioning

confidence: 98%

Li₃[ScN₂]: The First Nitridoscandate(III)—Tetrahedral Sc Coordination and Unusual MX₂ Framework

Niewa

Zherebtsov

Leoni

2003

Chemistry A European J

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“…The structure of 10 (see Figure S25 in the Supporting Information) is very similar to that of 9 , except there is one less molecule of THF coordinated, resulting in an extremely close Yb–C distance (2.431(7) Å) that indicates the formation of a Yb–C single bond by cyclometalation. Previous examples of cyclometalated Yb silylamides have Yb–C lengths from 2.359(5) to 2.42(2) Å, though these all have a potassium cation in close proximity to the carbon atom bound to Yb. , The structure of 10 is disordered about the Yb atom, while the ligands remain essentially stationary. This necessitated modeling the two close carbons (C(1) and C(20)) over two positions with equivalent xyz coordinates and occupancies tied to Yb(1A) and Yb(1B).…”

Section: Resultsmentioning

confidence: 99%

“…As with 1−4, the FTIR spectra of 5 and 7 each showed a characteristic absorption at 935 cm −1 , 5) to 2.42(2) Å, though these all have a potassium cation in close proximity to the carbon atom bound to Yb. 15,34 The structure of 10 is disordered about the Yb atom, while the ligands remain essentially stationary. This necessitated modeling the two close carbons (C(1) and C( 20)) over two positions with equivalent xyz coordinates and occupancies tied to Yb(1A) and Yb(1B).…”

Section: ■ Resultsmentioning

confidence: 99%

Investigation into the Effects of a Trigonal-Planar Ligand Field on the Electronic Properties of Lanthanide(II) Tris(silylamide) Complexes (Ln = Sm, Eu, Tm, Yb)

et al. 2017

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In recent work we have reported the synthesis and physical properties of near-linear Ln(II) (Ln = lanthanide) complexes utilizing the bulky bis(silylamide) {N(SiPr)}. Herein, we synthesize trigonal-planar Ln(II) complexes by employing a smaller bis(silylamide), {N(SiBuMe)} (N**), to study the effects of this relatively rare Ln geometry/oxidation state combination on the magnetic and optical properties of complexes. We show that the charge-separated trigonal-planar Ln(II) complexes [K(2.2.2-cryptand)][Ln(N**)] (Ln = Sm (1), Eu (2), Tm (3), Yb (4)) can be prepared by the reaction of 1.5 equiv of [{K(N**)}] with LnITHF (Ln = Sm, Yb) or LnI (Ln = Eu, Tm) and 1 equiv of 2.2.2-cryptand in EtO. Complex 3 is the first structurally characterized trigonal-planar Tm(II) complex. In the absence of 2.2.2-cryptand, [K(DME)][Sm(N**)] (5) and [Ln(N**)(μ-N**)K(toluene)] (Ln = Sm (6), Eu (7)) were isolated in the presence of DME (dimethoxyethane) or toluene, respectively. The 1:1 reaction of [{K(N**)}] with LnITHF (Ln = Sm, Yb) in THF gave the four-coordinate pseudo-tetrahedral Lewis base adducts [Ln(N**)(THF)] (Ln = Sm (8), Yb (9)) and the cyclometalated complex [Yb(N**){N(SiBuMe)(SiBuMeCH)}(THF)] (10). Complexes 1-10 have been characterized as appropriate by single-crystal XRD, magnetic measurements, multinuclear NMR, EPR, and electronic spectroscopy, together with CASSCF-SO and DFT calculations. The physical properties of 1-4 are compared and contrasted with those of closely related near-linear Ln(II) bis(silylamide) complexes.

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“…Nearly always the former bond angles approach 90°, whereas 168 a [Na(THF){(2,6-i Pr2C6H3N(SiMe3)}Al(CtCPh)3)]2 32 89 a 171 a [K(THF){(2,6-i Pr2C6H3N(SiMe3)}Al(CtCPh)3)]2 32 96.2 a 171 a [Li(dioxane){(2,6-i Pr2C6H3N(SiMe3)}Al(CtCPh)3)]2(dioxane) 32 90 a 170 a [(12-crown-4)2Na{Zn(THF)(CtCPh)3}] 33 175 a [Li2{(CtCPh)3Mg(TMEDA)}2] 34 167.8( 4 7), as the lanthanide is surrounded by three bulky amido ligands in addition to the acetylide. 28 In 12, the Na binds side-on to the PhCtCligand with an RC-Na-βC angle of only 26.30(11)°.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structural Authentication, and Structurally Defined Metalation Reactions of Lithium and Sodium DA-Zincate Bases (DA = diisopropylamide) with Phenylacetylene

Clegg

García‐Álvarez

et al. 2008

Organometallics

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In a study aimed at developing the diisopropylamido (DA) chemistry of zincates, the new lithium DA-zincate [(TMEDA) • Li( t Bu)(DA)Zn( t Bu)] (4) has been synthesized by an interlocking cocomplexation approach comprising mixing of its three component chemicals, LDA, t Bu 2 Zn, and TMEDA, in a 1:1:1 ratio in hexane solution. Previously made by transamination from the corresponding TMP-zincate, the known sodium congener [(TMEDA) • Na( t Bu)(DA)Zn( t Bu)] (2) was also synthesized by this approach, substituting NaDA for LDA. Closely resembling each other, their molecular structures determined by X-ray crystallography can be categorized as contact ion-pair ates of TMEDA-chelated alkali metal cations linked to trigonal-planar dialkyl-Zn anions via bridging DA ligands. Reaction of 4 and 2 with phenylacetylene affords the bimetallic acetylides [{(TMEDA) • Li(CtCPh) 2 Zn( t Bu)} 2 • (TMEDA)] ( 5) and [{(TMEDA) • Na(CtCPh) 2 Zn( t Bu)} 2 ] (6), respectively. X-ray crystallographic studies reveal 5 is a pseudodimer (tetranuclear) with two (LiCZnC) rings linked at the Zn atoms by a bridging, nonchelating TMEDA ligand; in contrast 6 adopts a distorted cubane of alternating PhCtC and metal (2 Na, 2 Zn) corners. For comparison, the synthesis and crystal structures of the neutral zinc complexes [(TMEDA) • Zn(CtCPh) 2 ] (7) and [(TMEDA) • Zn( t Bu)(CtCPh)] ( 8), formally components of the ate complexes 5 and 6, are also reported. In addition, the 1 H and 13 C NMR spectra of 2, 4, 5, 6, 7, and 8 recorded from solutions in C 6 D 6 are disclosed.

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Die Deprotonierung silylierter Amido-Komplexe von Seltenerdelementen

Cited by 16 publications

References 0 publications

Li₃[ScN₂]: The First Nitridoscandate(III)—Tetrahedral Sc Coordination and Unusual MX₂ Framework

Li₃[ScN₂]: The First Nitridoscandate(III)—Tetrahedral Sc Coordination and Unusual MX₂ Framework

Investigation into the Effects of a Trigonal-Planar Ligand Field on the Electronic Properties of Lanthanide(II) Tris(silylamide) Complexes (Ln = Sm, Eu, Tm, Yb)

Synthesis, Structural Authentication, and Structurally Defined Metalation Reactions of Lithium and Sodium DA-Zincate Bases (DA = diisopropylamide) with Phenylacetylene

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Die Deprotonierung silylierter Amido-Komplexe von Seltenerdelementen

Cited by 16 publications

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Li3[ScN2]: The First Nitridoscandate(III)—Tetrahedral Sc Coordination and Unusual MX2 Framework

Li3[ScN2]: The First Nitridoscandate(III)—Tetrahedral Sc Coordination and Unusual MX2 Framework

Investigation into the Effects of a Trigonal-Planar Ligand Field on the Electronic Properties of Lanthanide(II) Tris(silylamide) Complexes (Ln = Sm, Eu, Tm, Yb)

Synthesis, Structural Authentication, and Structurally Defined Metalation Reactions of Lithium and Sodium DA-Zincate Bases (DA = diisopropylamide) with Phenylacetylene

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Li₃[ScN₂]: The First Nitridoscandate(III)—Tetrahedral Sc Coordination and Unusual MX₂ Framework

Li₃[ScN₂]: The First Nitridoscandate(III)—Tetrahedral Sc Coordination and Unusual MX₂ Framework