Hexacoordinate Silicon Compounds with a Dianionic Tetradentate (N,N′,N′,N)-Chelating Ligand

Gerlach, Daniela; Brendler, Erica; Wagler, Jörg

doi:10.3390/inorganics4020008

Cited by 5 publications

(2 citation statements)

References 116 publications

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“…29 Gerlach, who conducted 76 qualitative interviews with women immigration detainees and former detainees in the UK, concluded that part of the harm stemmed from the indignity associated with 'the disconnect between their own perceived sense of being a "good" person, and their treatment at the hands of the Home Office'. 30 This was also concluded by Rivas and Bull, who examined the experiences of women held in long-term immigration detention in Australia. 31 They also found that women detainees 'experience this detention differently than their male counterparts'.…”

Section: The Harms Of Arbitrary Detentionmentioning

confidence: 74%

“Arbitrariness” as an Indication of Harm

Ferstman

2024

Conceptualising Arbitrary Detention

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Section: The Harms Of Arbitrary Detentionmentioning

confidence: 74%

“Arbitrariness” as an Indication of Harm

Ferstman

2024

Conceptualising Arbitrary Detention

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“…The Si-C bond (1.853(4) Å) is only marginally longer than in the starting silane MeSi(pyO) 3 (1.837(2) Å), thus hinting at only a weak Pd→Si lone pair donor action. At hexacoordinate silicon with trans-disposed stronger donor (e.g., another hydrocarbyl group [42,43], 2-pyridinethiolato N atom [28] or 8-oxyquinolinyl N atom [44,45]), one would expect a Si-C bond lengthening beyond 1.90 Å. The Pd-Cl bond (2.891(1) Å), however, is unexpectedly long, thus hinting at ionic dissociation.…”

Section: Reactions Of Mesi(pyo)3 With [Pdcl2(ncme)2] and Cuclmentioning

confidence: 99%

(2-Pyridyloxy)silanes as Ligands in Transition Metal Coordination Chemistry

et al. 2018

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Proceeding our initial studies of compounds with formally dative TM→Si bonds (TM = Ni, Pd, Pt), which feature a paddlewheel arrangement of four (N,S) or (N,N) bridging ligands around the TM–Si axis, the current study shows that the (N,O)-bidentate ligand 2-pyridyloxy (pyO) is also capable of bridging systems with TM→Si bonds (shown for TM = Pd, Cu). Reactions of MeSi(pyO)3 with [PdCl2(NCMe)2] and CuCl afforded the compounds MeSi(µ-pyO)4PdCl (1) and MeSi(µ-pyO)3CuCl (2), respectively. In the latter case, some crystals of the Cu(II) compound MeSi(µ-pyO)4CuCl (3) were obtained as a byproduct. Analogous reactions of Si(pyO)4, in the presence of HpyO, with [PdCl2(NCMe)2] and CuCl2, afforded the compounds [(HpyO)Si(µ-pyO)4PdCl]Cl (4), (HpyO)2Si[(µ-pyO)2PdCl2]2 (5), and (HpyO)2Si[(µ-pyO)2CuCl2]2 (6), respectively. Compounds 1–6 and the starting silanes MeSi(pyO)3 and Si(pyO)4 were characterized by single-crystal X-ray diffraction analyses and, with exception of the paramagnetic compounds 3 and 6, with NMR spectroscopy. Compound 2 features a pentacoordinate Si atom, the Si atoms of the other complexes are hexacoordinate. Whereas compounds 1–4 feature a TM→Si bond each, the Si atoms of compounds 5 and 6 are situated in an O6 coordination sphere, while the TMCl2 groups are coordinated to pyridine moieties in the periphery of the molecule. The TM–Si interatomic distances in compounds 1–4 are close to the sum of the covalent radii (1 and 4) or at least significantly shorter than the sum of the van-der-Waals radii (2 and 3). The latter indicates a noticeably weaker interaction for TM = Cu. For the series 1, 2, and 3, all of which feature the Me–Si motif trans-disposed to the TM→Si bond, the dependence of the TM→Si interaction on the nature of TM (Pd(II), Cu(I), and Cu(II)) was analyzed using quantum chemical calculations, that is, the natural localized molecular orbitals (NLMO) analyses, the non-covalent interaction (NCI) descriptor, Wiberg bond order (WBO), and topological characteristics of the bond critical points using the atoms in molecules (AIM) approach.

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New N – heterocyclic mono – and disilavinylidene iron – complexes by density functional theory

Purlak

Kassaee

2020

J of Physical Organic Chem

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Recently, we found less nucleophilicity (N) for normally and abnormally disubstituted Arduengo‐type monosilylenes [R2N4Si:] (1–10) than their corresponding disilavinylidene ligands [R2N4SiSi:] (1′–10′). Considering the importance of silylene–iron complexes, here we compare and contrast thermodynamic properties of their novel [R2N4Si: → Fe(N(SiH3)2)2] (1c–10c) and [R2N4SiSi: → Fe(N(SiH3)2)2] iron complexes (1′c–10′c), for R = H, Me, ethyl, i‐propyl, and t‐butyl, at B3LYP/6‐311++G**+ LANL2DZ level of theory. Isodesmic reactions show higher stability for disilavinylidenes 1′c–10′c compared with their corresponding monosilylene 1c–10c. In all species, the natural bond orbital (NBO) calculations show transfer of charge from the silylene (of the ligand) to iron(II). Multiple Fe–Si bonding character is detected in all complexes (Wiberg bond index > 1). Yet Fe–Si bond distances in 1′c–10′c appear shorter than those in their corresponding 1c–10c. Binding energy (ΔEbin) of [Fe(N(SiH3)2)2] with 1′–10′ appears higher in 1′c–10′c than the corresponding 1c–10c.

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Hexacoordinate Silicon Compounds with a Dianionic Tetradentate (N,N′,N′,N)-Chelating Ligand

Cited by 5 publications

References 116 publications

“Arbitrariness” as an Indication of Harm

“Arbitrariness” as an Indication of Harm

(2-Pyridyloxy)silanes as Ligands in Transition Metal Coordination Chemistry

New N – heterocyclic mono – and disilavinylidene iron – complexes by density functional theory

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