Tp*Cu(<scp>i</scp>)–CN–SiL<sub>2</sub>–NC–Cu(<scp>i</scp>)Tp* – a hexacoordinate Si-complex as connector for redox active metals via π-conjugated ligands

Kämpfe, Alexander; Brendler, Erica; Kroke, Edwin; Wagler, Jörg

doi:10.1039/c4dt03903c

Cited by 9 publications

(4 citation statements)

References 46 publications

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“…The better part of the existing compounds with an N ‐pyrrolylsilyl substructure is being studied in the form of 1) phthalocyanines, porphyrins, and analogues thereof; 2) silyl‐protected pyrroles (mainly R 3 SiPyr where R=alkyl or aryl); or 3) chemical vapor deposition (CVD) precursors (Pyr n SiH (4− n ) ; n =1–3) . Furthermore, three research groups have specifically studied the structure and reactivity of pyrrolylsilane derivatives (Scheme ): the dihydroxyphenol dipyrrin ( I ) by Sakamoto et al., the (NNO) pyrrolehydroxyphenol carbaldimine ( II ) by Gerlach et al., and dipyrrins ( III ) and acylpyrroles ( IV ) by Kämpfe et al . Interestingly, the latter comment that the acyl moiety in IV does not undergo hydrosilylation; the acylpyrrolide hydrosilanes involved during the preparation of IV preferentially liberate H 2 upon reaction with the second ligand.…”

Section: Introductionmentioning

confidence: 99%

Hydrosilylation in Aryliminopyrrolide‐Substituted Silanes

Witteman

Evers

Zhan

et al. 2016

Chemistry A European J

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A range of silanes was synthesized by the reaction of HSiCl3 with iminopyrrole derivatives in the presence of NEt3 . In certain cases, intramolecular hydrosilylation converts the imine ligand into an amino substituent. This reaction is inhibited by factors such as electron-donating substitution on Si and steric bulk. The monosubstituted ((Dipp) IMP)SiHMeCl ((Dipp) IMP=2-[N-(2,6-diisopropylphenyl)iminomethyl]pyrrolide), is stable towards hydrosilylation, but slow hydrosilylation is observed for ((Dipp) IMP)SiHCl2 . Reaction of two equivalents of (Dipp) IMPH with HSiCl3 results in the hydrosilylation product ((Dipp) AMP)((Dipp) IMP)SiCl ((Dipp) AMP=2-[N-(2,6-diisopropylphenyl)aminomethylene]pyrrolide), but the trisubsitituted ((Dipp) IMP)3 SiH is stable. Monitoring the hydrosilylation reaction of ((Dipp) IMP)SiHCl2 reveals a reactive pathway involving ligand redistribution reactions to form the disubstituted ((Dipp) AMP)((Dipp) IMP)SiCl as an intermediate. The reaction is strongly accelerated in the presence of chloride anions.

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Section: Introductionmentioning

confidence: 99%

Hydrosilylation in Aryliminopyrrolide‐Substituted Silanes

Witteman

Evers

Zhan

et al. 2016

Chemistry A European J

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“…Starting materials, 1Ge [ 22 ] and CuCl [ 33 ], were available from previous studies. Diethyl ether was dried using an MBraun SPS-800 setup (MBraun, Garching, Germany).…”

Section: Methodsmentioning

confidence: 99%

Ge–Cu-Complexes Ph(pyO)Ge(μ2-pyO)2CuCl and PhGe(μ2-pyO)4CuCl—Representatives of Cu(I)→Ge(IV) and Cu(II)→Ge(IV) Dative Bond Systems

Wagler

Gericke

2023

Molecules

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Phenylgermaniumpyridine-2-olate PhGe(pyO)3 (compound 1Ge) and CuCl react with the formation of the heteronuclear complex Ph(pyO)Ge(μ2-pyO)2CuCl (2Ge’) rather than forming the expected compound PhGe(μ2-pyO)3CuCl (2Ge). Single-point calculations (at the B2T-PLYP level) of the optimized molecular structures confirmed the relative stability of isomer 2Ge’ over 2Ge and, for the related silicon congeners, the relative stability of 2Si over 2Si’. Decomposition of a solution of 2Ge’ upon access to air provided access to some crystals of the copper(II) compound PhGe(μ2-pyO)4CuCl (3Ge). Compounds 2Ge’ and 3Ge were characterized by single-crystal X-ray diffraction analyses, and the Ge–Cu bonds in these compounds were analyzed with the aid of quantum chemical calculations, e.g., Natural Bond Orbital analyses (NBO), Non-Covalent Interactions descriptor (NCI), and topology of the electron density at bond critical point using Quantum Theory of Atoms-In-Molecules (QTAIM) in conjunction with the related silicon compounds PhSi(μ2-pyO)3CuCl (2Si), PhSi(μ2-pyO)4CuCl (3Si), as well as the potential isomers Ph(pyO)Si(μ2-pyO)2CuCl (2Si’) and PhGe(μ2-pyO)3CuCl (2Ge). Pronounced Cu→Ge (over Cu→Si) lone pair donation was found for the Cu(I) compounds, whereas in Cu(II) compounds 3Si and 3Ge, this σ-donation is less pronounced and only marginally enhanced in 3Ge over 3Si.

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“…2-Trimethylsiloxypyridine [26] was synthesized according to a literature procedure. [PdCl 2 (NCMe) 2 ] [8] and CuCl [55] were available in the laboratory from previous studies. The solution NMR spectra ( 1 H, 13 C, 29 Si) were recorded on Bruker Avance III 500 MHz and Bruker Nanobay 400 MHz spectrometers (Bruker Biospin, Rheinstetten, Germany) and Me 4 Si was used as internal standard.…”

Section: General Considerationsmentioning

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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TpCu(i)–CN–SiL₂–NC–Cu(i)Tp – a hexacoordinate Si-complex as connector for redox active metals via π-conjugated ligands

Cited by 9 publications

References 46 publications

Hydrosilylation in Aryliminopyrrolide‐Substituted Silanes

Hydrosilylation in Aryliminopyrrolide‐Substituted Silanes

Ge–Cu-Complexes Ph(pyO)Ge(μ2-pyO)2CuCl and PhGe(μ2-pyO)4CuCl—Representatives of Cu(I)→Ge(IV) and Cu(II)→Ge(IV) Dative Bond Systems

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

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Tp*Cu(i)–CN–SiL2–NC–Cu(i)Tp* – a hexacoordinate Si-complex as connector for redox active metals via π-conjugated ligands

Cited by 9 publications

References 46 publications

Hydrosilylation in Aryliminopyrrolide‐Substituted Silanes

Hydrosilylation in Aryliminopyrrolide‐Substituted Silanes

Ge–Cu-Complexes Ph(pyO)Ge(μ2-pyO)2CuCl and PhGe(μ2-pyO)4CuCl—Representatives of Cu(I)→Ge(IV) and Cu(II)→Ge(IV) Dative Bond Systems

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

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TpCu(i)–CN–SiL₂–NC–Cu(i)Tp – a hexacoordinate Si-complex as connector for redox active metals via π-conjugated ligands