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

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 ?-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) .

SUBMITTER: Zitz R

PROVIDER: S-EPMC4389698 | biostudies-literature | 2015 Apr

REPOSITORIES: biostudies-literature

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

Zitz Rainer R Arp Henning H Hlina Johann J Walewska Małgorzata M Marschner Christoph C Szilvási Tibor T Blom Burgert B Baumgartner Judith J

Inorganic chemistry 20150310 7

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 meta ...[more]

PMID: 25756230

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Project description:Manganese disilyl hydride complexes [(dmpe)2MnH(SiH2R)2] (4Ph : R = Ph, 4Bu : R = n Bu) reacted with ethylene to form silene hydride complexes [(dmpe)2MnH(RHSi[double bond, length as m-dash]CHMe)] (6Ph,H : R = Ph, 6Bu,H : R = n Bu). Compounds 6R,H reacted with a second equivalent of ethylene to generate [(dmpe)2MnH(REtSi[double bond, length as m-dash]CHMe)] (6Ph,Et : R = Ph, 6Bu,Et : R = n Bu), resulting from apparent ethylene insertion into the silene Si-H bond. Furthermore, in the absence of ethylene, silene complex 6Bu,H slowly isomerized to the silylene hydride complex [(dmpe)2MnH([double bond, length as m-dash]SiEt n Bu)] (3Bu,Et ). Reactions of 4R with ethylene likely proceed via low-coordinate silyl {[(dmpe)2Mn(SiH2R)] (2Ph : R = Ph, 2Bu : R = n Bu)} or silylene hydride {[(dmpe)2MnH([double bond, length as m-dash]SiHR)] (3Ph,H : R = Ph, 3Bu,H : R = n Bu)} intermediates accessed from 4R by H3SiR elimination. DFT calculations and high temperature NMR spectra support the accessibility of these intermediates, and reactions of 4R with isonitriles or N-heterocyclic carbenes yielded the silyl isonitrile complexes [(dmpe)2Mn(SiH2R)(CNR')] (7a-d: R = Ph or n Bu; R' = o-xylyl or t Bu), and NHC-stabilized silylene hydride complexes [(dmpe)2MnH{[double bond, length as m-dash]SiHR(NHC)}] (8a-d: R = Ph or n Bu; NHC = 1,3-diisopropylimidazolin-2-ylidene or 1,3,4,5-tetramethyl-4-imidazolin-2-ylidene), respectively, all of which were crystallographically characterized. Silyl, silylene and silene complexes in this work were accessed via reactions of [(dmpe)2MnH(C2H4)] (1) with hydrosilanes, in some cases followed by ethylene. Therefore, ethylene (C2H4 and C2D4) hydrosilylation was investigated using [(dmpe)2MnH(C2H4)] (1) as a pre-catalyst, resulting in stepwise conversion of primary to secondary to tertiary hydrosilanes. Various catalytically active manganese-containing species were observed during catalysis, including silylene and silene complexes, and a catalytic cycle is proposed.

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Dataset Information

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

Publications

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

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