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Open-shell lanthanide(II+) or -(III+) complexes bearing σ-silyl and silylene ligands: synthesis, structure, and bonding analysis.

Zitz R, Arp H, Hlina J, Walewska M, Marschner C, Szilvási T, Blom B, Baumgartner J - Inorg Chem (2015)

Bottom Line: Density functional theory calculations were carried out for complexes 2a-2d, 5, and 6 to elucidate the bonding situation between the Ln(II+) or Ln(III+) centers and Si.In particular, a decrease in the Mayer bond order (MBO) of the Ln-Si bond is observed in the series 2a-2d in moving from the lighter to the heavier lanthanides (Tm = 0.53, Ho = 0.62, Tb = 0.65, and Gd = 0.75), which might indicate decreasing covalency in the Ln-Si bond.In accordance with the long bond lengths observed experimentally in complexes 5 and 6, comparatively low MBOs were determined for both silylene complexes (5, 0.24; 6, 0.25) .

View Article: PubMed Central - PubMed

Affiliation: †Institut für Anorganische Chemie, Technische Universität Graz, Stremayrgasse 9, 8010 Graz, Austria.

ABSTRACT
Complexes featuring lanthanide (Ln)-Si bonds represent a highly neglected research area. Herein, we report a series of open-shell Ln(II+) and Ln(III+) complexes bearing σ-bonded silyl and base-stabilized N-heterocyclic silylene (NHSi) ligands. The reactions of the Ln(III+) complexes Cp3Ln (Ln = Tm, Ho, Tb, Gd; Cp = cyclopentadienide) with the 18-crown-6 (18-cr-6)-stabilized 1,4-oligosilanyl dianion [(18-cr-6)KSi(SiMe3)2SiMe2SiMe2Si(SiMe3)2K(18-cr-6)] (1) selectively afford the corresponding metallacyclopentasilane salts [Cp2Ln({Si(SiMe3)2SiMe2}2)](-)[K2(18-cr-6)2Cp](+) [Ln = Tm (2a), Ho (2b), Tb (2c), Gd (2d)]. Complexes 2a-2d represent the first examples of structurally characterized Tm, Ho, Tb, and Gd complexes featuring Ln-Si bonds. Strikingly, the analogous reaction of 1 with the lighter element analogue Cp3Ce affords the acyclic product [Cp3CeSi(SiMe3)2SiMe2SiMe2Si(SiMe3)2-Cp3Ce](2-)2[K(18-cr-6)](+) (3) as the first example of a complex featuring a Ce-Si bond. In an alternative synthetic approach, the aryloxy-functionalized benzamidinato NHSi ligand Si(OC6H4-2-tBu){(NtBu)2CPh} (4a) and the alkoxy analogue Si(OtBu){(NtBu)2CPh} (4b) were reacted with Cp*2Sm(OEt2), affording, by OEt2 elimination, the corresponding silylene complexes, both featuring Sm(II+) centers: Cp*2Sm ← :Si(O-C6H4-2-tBu){(NtBu)2CPh} (6) and Cp*2Sm ← :Si(OtBu){(NtBu)2CPh} (5). Complexes 5 and 6 are the first four-coordinate silylene complexes of any f-block element to date. All complexes were fully characterized by spectroscopic means and by single-crystal X-ray diffraction analysis. In the series 2a-2d, a linear correlation was observed between the Ln-Si bond lengths and the covalent radii of the corresponding Ln metals. Moreover, in complexes 5 and 6, notably long Sm-Si bonds are observed, in accordance with a donor-acceptor interaction between Si and Sm [5, 3.4396(15) Å; 6, 3.3142(18) Å]. Density functional theory calculations were carried out for complexes 2a-2d, 5, and 6 to elucidate the bonding situation between the Ln(II+) or Ln(III+) centers and Si. In particular, a decrease in the Mayer bond order (MBO) of the Ln-Si bond is observed in the series 2a-2d in moving from the lighter to the heavier lanthanides (Tm = 0.53, Ho = 0.62, Tb = 0.65, and Gd = 0.75), which might indicate decreasing covalency in the Ln-Si bond. In accordance with the long bond lengths observed experimentally in complexes 5 and 6, comparatively low MBOs were determined for both silylene complexes (5, 0.24; 6, 0.25) .

No MeSH data available.


Molecularstructure of 3 (thermal ellipsoid plot drawn at the 30%probability level). All hydrogen atoms are omitted for clarity. Bondlengths (Å) and angles (deg): Ce1–C1 2.817(3), Ce1–C62.844(3), Ce1–Si1 3.2283(2), Si1–Si4 2.3601(15), Si1–Si32.3784(13), Si1–Si2 2.3981(13); Si4–Si1–Si3 99.54(5),Si4–Si1–Si2 102.43(6), Si3–Si1–Si2 98.81(5),Si4–Si1–Ce1 115.26(5), Si3–Si1–Ce1 111.43(4),Si2–Si1–Ce1 125.37(5).
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fig3: Molecularstructure of 3 (thermal ellipsoid plot drawn at the 30%probability level). All hydrogen atoms are omitted for clarity. Bondlengths (Å) and angles (deg): Ce1–C1 2.817(3), Ce1–C62.844(3), Ce1–Si1 3.2283(2), Si1–Si4 2.3601(15), Si1–Si32.3784(13), Si1–Si2 2.3981(13); Si4–Si1–Si3 99.54(5),Si4–Si1–Si2 102.43(6), Si3–Si1–Si2 98.81(5),Si4–Si1–Ce1 115.26(5), Si3–Si1–Ce1 111.43(4),Si2–Si1–Ce1 125.37(5).

Mentions: In all four structures, the ionpairs are separated. The countercation (18-cr-6)K-Cp-K(18-cr-6) showsdisorder in one crown ether for 2b and in both crownethers for 2a and 2d, a fact that is reflectedby the number of restraints used. The Ce complex 3 (Figure 3) crystallized in the triclinic space group P1̅ with an additional toluene molecule in the asymmetricunit. One of the Cp ligands coordinates to the cationic moiety K/18-cr-6/THF.


Open-shell lanthanide(II+) or -(III+) complexes bearing σ-silyl and silylene ligands: synthesis, structure, and bonding analysis.

Zitz R, Arp H, Hlina J, Walewska M, Marschner C, Szilvási T, Blom B, Baumgartner J - Inorg Chem (2015)

Molecularstructure of 3 (thermal ellipsoid plot drawn at the 30%probability level). All hydrogen atoms are omitted for clarity. Bondlengths (Å) and angles (deg): Ce1–C1 2.817(3), Ce1–C62.844(3), Ce1–Si1 3.2283(2), Si1–Si4 2.3601(15), Si1–Si32.3784(13), Si1–Si2 2.3981(13); Si4–Si1–Si3 99.54(5),Si4–Si1–Si2 102.43(6), Si3–Si1–Si2 98.81(5),Si4–Si1–Ce1 115.26(5), Si3–Si1–Ce1 111.43(4),Si2–Si1–Ce1 125.37(5).
© Copyright Policy
Related In: Results  -  Collection

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Show All Figures
getmorefigures.php?uid=PMC4389698&req=5

fig3: Molecularstructure of 3 (thermal ellipsoid plot drawn at the 30%probability level). All hydrogen atoms are omitted for clarity. Bondlengths (Å) and angles (deg): Ce1–C1 2.817(3), Ce1–C62.844(3), Ce1–Si1 3.2283(2), Si1–Si4 2.3601(15), Si1–Si32.3784(13), Si1–Si2 2.3981(13); Si4–Si1–Si3 99.54(5),Si4–Si1–Si2 102.43(6), Si3–Si1–Si2 98.81(5),Si4–Si1–Ce1 115.26(5), Si3–Si1–Ce1 111.43(4),Si2–Si1–Ce1 125.37(5).
Mentions: In all four structures, the ionpairs are separated. The countercation (18-cr-6)K-Cp-K(18-cr-6) showsdisorder in one crown ether for 2b and in both crownethers for 2a and 2d, a fact that is reflectedby the number of restraints used. The Ce complex 3 (Figure 3) crystallized in the triclinic space group P1̅ with an additional toluene molecule in the asymmetricunit. One of the Cp ligands coordinates to the cationic moiety K/18-cr-6/THF.

Bottom Line: Density functional theory calculations were carried out for complexes 2a-2d, 5, and 6 to elucidate the bonding situation between the Ln(II+) or Ln(III+) centers and Si.In particular, a decrease in the Mayer bond order (MBO) of the Ln-Si bond is observed in the series 2a-2d in moving from the lighter to the heavier lanthanides (Tm = 0.53, Ho = 0.62, Tb = 0.65, and Gd = 0.75), which might indicate decreasing covalency in the Ln-Si bond.In accordance with the long bond lengths observed experimentally in complexes 5 and 6, comparatively low MBOs were determined for both silylene complexes (5, 0.24; 6, 0.25) .

View Article: PubMed Central - PubMed

Affiliation: †Institut für Anorganische Chemie, Technische Universität Graz, Stremayrgasse 9, 8010 Graz, Austria.

ABSTRACT
Complexes featuring lanthanide (Ln)-Si bonds represent a highly neglected research area. Herein, we report a series of open-shell Ln(II+) and Ln(III+) complexes bearing σ-bonded silyl and base-stabilized N-heterocyclic silylene (NHSi) ligands. The reactions of the Ln(III+) complexes Cp3Ln (Ln = Tm, Ho, Tb, Gd; Cp = cyclopentadienide) with the 18-crown-6 (18-cr-6)-stabilized 1,4-oligosilanyl dianion [(18-cr-6)KSi(SiMe3)2SiMe2SiMe2Si(SiMe3)2K(18-cr-6)] (1) selectively afford the corresponding metallacyclopentasilane salts [Cp2Ln({Si(SiMe3)2SiMe2}2)](-)[K2(18-cr-6)2Cp](+) [Ln = Tm (2a), Ho (2b), Tb (2c), Gd (2d)]. Complexes 2a-2d represent the first examples of structurally characterized Tm, Ho, Tb, and Gd complexes featuring Ln-Si bonds. Strikingly, the analogous reaction of 1 with the lighter element analogue Cp3Ce affords the acyclic product [Cp3CeSi(SiMe3)2SiMe2SiMe2Si(SiMe3)2-Cp3Ce](2-)2[K(18-cr-6)](+) (3) as the first example of a complex featuring a Ce-Si bond. In an alternative synthetic approach, the aryloxy-functionalized benzamidinato NHSi ligand Si(OC6H4-2-tBu){(NtBu)2CPh} (4a) and the alkoxy analogue Si(OtBu){(NtBu)2CPh} (4b) were reacted with Cp*2Sm(OEt2), affording, by OEt2 elimination, the corresponding silylene complexes, both featuring Sm(II+) centers: Cp*2Sm ← :Si(O-C6H4-2-tBu){(NtBu)2CPh} (6) and Cp*2Sm ← :Si(OtBu){(NtBu)2CPh} (5). Complexes 5 and 6 are the first four-coordinate silylene complexes of any f-block element to date. All complexes were fully characterized by spectroscopic means and by single-crystal X-ray diffraction analysis. In the series 2a-2d, a linear correlation was observed between the Ln-Si bond lengths and the covalent radii of the corresponding Ln metals. Moreover, in complexes 5 and 6, notably long Sm-Si bonds are observed, in accordance with a donor-acceptor interaction between Si and Sm [5, 3.4396(15) Å; 6, 3.3142(18) Å]. Density functional theory calculations were carried out for complexes 2a-2d, 5, and 6 to elucidate the bonding situation between the Ln(II+) or Ln(III+) centers and Si. In particular, a decrease in the Mayer bond order (MBO) of the Ln-Si bond is observed in the series 2a-2d in moving from the lighter to the heavier lanthanides (Tm = 0.53, Ho = 0.62, Tb = 0.65, and Gd = 0.75), which might indicate decreasing covalency in the Ln-Si bond. In accordance with the long bond lengths observed experimentally in complexes 5 and 6, comparatively low MBOs were determined for both silylene complexes (5, 0.24; 6, 0.25) .

No MeSH data available.