Synthesis of a α-Chlorosilyl Functionalized Donor-Stabilized Chlorogermylene

Dhara, Debabrata; Hüch, Volker; Scheschkewitz, David; Jana, Anukul

doi:10.3390/inorganics6010006

Cited by 3 publications

(4 citation statements)

References 32 publications

(46 reference statements)

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“…Scheschkewitz and co-workers showed that West’s N -heterocyclic silylene readily inserts in the Ge–Cl bond of the dichlorogermylene (I i Pr 2 Me 2 )GeCl 2 ( 759b ), furnishing the silyl-substituted germylene 801 (Figure ). In comparison to the starting material, the 29 Si NMR signal is strongly downfield-shifted from −3.4 to 78.3 ppm. The C NHC –Ge bond length (2.081 Å) is within the expected range.…”

Section: Nhc Complexes Of Main Group Elementsmentioning

confidence: 99%

NHCs in Main Group Chemistry

et al. 2018

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Since the discovery of the first stable N-heterocyclic carbene (NHC) in the beginning of the 1990s, these divalent carbon species have become a common and available class of compounds, which have found numerous applications in academic and industrial research. Their important role as two-electron donor ligands, especially in transition metal chemistry and catalysis, is difficult to overestimate. In the past decade, there has been tremendous research attention given to the chemistry of low-coordinate main group element compounds. Significant progress has been achieved in stabilization and isolation of such species as Lewis acid/base adducts with highly tunable NHC ligands. This has allowed investigation of numerous novel types of compounds with unique electronic structures and opened new opportunities in the rational design of novel organic catalysts and materials. This Review gives a general overview of this research, basic synthetic approaches, key features of NHC-main group element adducts, and might be useful for the broad research community.

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Section: Nhc Complexes Of Main Group Elementsmentioning

confidence: 99%

NHCs in Main Group Chemistry

et al. 2018

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“…The slight upfield shift compared to the parent tetragermadiene 1 (4.27 ppm) [58] and silyldigermenes and ‐germylenes in general (13.5 to −2.7 ppm) [27,58,61,62] is in line with a certain donation of the germanium‐centered lone pairs of 4 to σ*‐orbitals at the SiMe 2 bridge. The characteristic 1 H and 13 C{ 1 H} signals of the Me 2 IPr methine groups (5.54 ppm) and the carbenic carbons (177.08, 177.00 ppm) confirm the coordination of Me 2 IPr to the germanium centers [19,20,23,27,28,63–67] . The GeTip 2 /Me 2 IPr adduct shows similar 1 H NMR septets at 5.64 and 5.34 ppm and a 13 C{ 1 H} resonance at 176.94 ppm for the coordinated Me 2 IPr.…”

Section: Resultsmentioning

confidence: 72%

“…The characteristic 1 H and 13 C{ 1 H} signals of the Me 2 IPr methine groups (5.54 ppm) and the carbenic carbons (177.08, 177.00 ppm) confirm the coordination of Me 2 IPr to the germanium centers. [19,20,23,27,28,[63][64][65][66][67] The GeTip 2 /Me 2 IPr adduct shows similar 1 H NMR septets at 5.64 and 5.34 ppm and a 13 C { 1 H} resonance at 176.94 ppm for the coordinated Me 2 IPr.…”

Section: Resultsmentioning

confidence: 91%

σ,π‐Conjugated Bis(germylene) Adducts with NHC and CAACs

Thoemmes

Morgenstern

Zimmer

et al. 2023

Chemistry A European J

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Heavier tetrylenes attract attention for their potential in synthesis, catalysis and small molecule activation. The coordination by N‐heterocyclic carbenes (NHCs) and cyclic (alkyl)(amino)carbenes (CAACs) results in substantial structural and electronic differences although typically only one of these yields stable derivatives for one and the same tetrylene. We now report both NHC‐ and CAAC‐coordination to a bridged bis(germylene) motif. The NHC‐coordinated bis(germylene) exhibits pyramidal germanium centers with lone pairs of electrons, while with CAAC an unprecedented stable bis(germene) with two Ge=C bonds is isolated. Spectroscopic and crystallographic evidence as well as DFT calculations confirm the effects of σ,π‐conjugation between the two germanium centers in both cases. The coordination of NHC is reversible as the reaction with BPh3 liberates the transient bis(germylene) and thus provides an alternative low‐temperature route towards polymers with Ge=Ge bonds.

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“…The enveloped geometry of the SiGe 2 C 2 ring skeleton was elucidated by XRD analysis. Jana, Scheschkewitz, and coworkers report on the synthesis of an NHC-adduct of chlorogermylene adjacent to an SiN 2 C 2 ring [15]. This was produced via the oxidative addition of West's N-heterocyclic silylene into the Ge-Cl bond of the NHC-complex of germanium(II) dichloride.…”

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confidence: 99%

Coordination Chemistry of Silicon

Inoue¹

2019

Inorganics

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It is with great pleasure to welcome readers to this Special Issue of Inorganics, devoted to "Coordination Chemistry of Silicon". Investigations into silicon compounds continue to afford a wealth of novel complexes, with unusual structures and brand-new reactivities. In fact, the ongoing quest for silicon complexes with novel properties has led to a large number of silicon compounds, that contain various types of ligands or substituents. Use of the divergent coordination behavior of silicon to construct sophisticated low-and hyper-valent silicon complexes makes it possible to change their electronic structures and properties. Therefore, progress of the coordination chemistry of silicon can be the key concept for the design and development of next generation silicon compound-based applications. This Special Issue is associated with the most recent advances in coordination chemistry of silicon with transition metals, as well as main group elements, including the stabilization of low-valent silicon species through the coordination of electron-donor ligands, such as N-heterocyclic carbenes (NHCs) and their derivatives [1,2]. This Special Issue is also dedicated to the development of novel synthetic methodologies, structural elucidations, bonding analyses, and possible applications in catalysis or chemical transformations, using related organosilicon compounds [3]. Besides, recent years have witnessed great research efforts in silicon-based polymer chemistry, as well as silicon surface chemistry, which have become increasingly important for unveiling the correlations between nanoscopic structural features and macroscopic material properties, including the coordination behavior at silicon.The 19 articles composing this Special Issue can be considered as a representative selection of the current research on this topic, reflecting the diversity of silicon chemistry and yield an impressive compilation.Intrinsic coordination behaviors of silanes towards transition metals are the subject of several articles in this issue. For example, Nakata et al. discuss the synthesis and structure of a hydrido platinum(II) complex with a dihydrosilyl ligand that bears a bulky 9-triptycyl group [4]. The ligand exchange reaction of this mononuclear (hydrido)(dihydrosilyl) complex with various phosphines has also been studied. Sunada and coworkers provide an elegant method for accessing planar tetrapalladium clusters starting from octa(isopropyl)cyclotetrasilane through the insertion of palladium atoms into the Si-Si bonds of the cyclotetrasilane [5]. While the ligand exchange reaction with NHCs yields the more coordinatively unsaturated cluster, reaction with a trimethylolpropane phosphite affords a planar tripalladium cluster. Wagler and coworkers demonstrate a striking coordination chemistry of (2-pyridyloxy)silanes with transition metals (Pd, Cu) [6]. The molecular structures of the complexes have been elucidated by crystallographic analysis, and further computational investigations provided an in-depth understanding of the interatomic ...

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Synthesis of a α-Chlorosilyl Functionalized Donor-Stabilized Chlorogermylene

Cited by 3 publications

References 32 publications

NHCs in Main Group Chemistry

NHCs in Main Group Chemistry

σ,π‐Conjugated Bis(germylene) Adducts with NHC and CAACs

Coordination Chemistry of Silicon

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