The Diverse Reactivity of Disilenes Toward Isocyanides

Tashkandi, Nada Y.; McOnie, Sarah L.; Bourque, Jeremy L.; Reinhold, Crispin R. W.; Baines, Kim M.

doi:10.1002/anie.201808490

Cited by 6 publications

(5 citation statements)

References 34 publications

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“…The reactivity of tetra mesityl disilene towards XylNC and tBuNC has been examined recently by Tashkandi et al [67] The investigators have isolated different products 143 and 144 for both isocyanides (Scheme 56). The insertion of two XylNC molecules across the Si=Si double bond of tetra mesityl disilene leads to 3-silaazetidine 143 (Scheme 56a) with the fourmembered ring SiC 2 N with C=Si, and C=N exocyclic bonds have been confirmed by single-crystal X-ray crystallography and 29 Si NMR spectroscopy.…”

Section: Siliconmentioning

confidence: 99%

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Coordination Chemistry of Main Group Metals with Organic Isocyanides

et al. 2022

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This review deals with advances in the chemistry of organic isocyanide complexes of the main group metals. Isocyanides acting as functional groups show a great dichotomy between nucleophilic and electrophilic characters, which diversifies the course of different multicomponent reactions. The carbon and nitrogen centers can serve as the donor atom in different metal isocyanide frameworks. Along with the variation in ligation properties and different coordination modes, the metalated isocyanides emerge as a well-established organometallic system with an effective synergistic mechanism, making them chemically and synthetically significant to chemists. However, the linear arrangement of the MÀ C=NÀ R induces the formation of multinuclear isocyanide complexes of good thermal stability, which draws the metalated isocyanides into the focal point of advanced reactivity and catalytic studies. A thorough literature survey on molecular main group metal complexes with organic isocyanides has been provided.

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Section: Siliconmentioning

confidence: 99%

“…The reactivity of tetra mesityl disilene towards XylNC and t BuNC has been examined recently by Tashkandi et al [67] . The investigators have isolated different products 143 and 144 for both isocyanides (Scheme 56).…”

Section: Reactivity Of Main Group Element Complexes Towards Isocyanidesmentioning

confidence: 99%

Coordination Chemistry of Main Group Metals with Organic Isocyanides

et al. 2022

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“…Despite the potential for parameter correlations between symmetry-related atoms, the reported bond lengths closely match those of 1. A second structure containing CNXyl was recently published in which CNXyl was cocrystallized with an iminodisilirane of interest (Tashkandi et al, 2019). In 1, the terminal C-N bond length and linear C-N-C angle (Table 2), as well as the solution IR CN stretch of 2117 cm À1 and the 13 C NMR resonance for the isocyanide C atom of 167.7 ppm, are consistent with a C N triple bond.…”

Section: Resultsmentioning

confidence: 92%

Crystal structures and spectroscopic characterization of MBr₂(CNXyl)_n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)₅ and Fe₂(CNXyl)₉

2019

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Structures and spectroscopic characterization of the divalent complexes cisdibromidotetrakis(2,6-dimethylphenyl isocyanide)iron(II) dichloromethane 0.771solvate, [FeBr 2 (C 9 H 9 N) 4 ]Á0.771CH 2 Cl 2 or cis-FeBr 2 (CNXyl) 4 Á0.771CH 2 Cl 2 (Xyl = 2,6-dimethylphenyl), trans-dibromidotetrakis(2,6-dimethylphenyl isocyanide)iron(II), [FeBr 2 (C 9 H 9 N) 4 ] or trans-FeBr 2 (CNXyl) 4 , trans-dibromidotetrakis(2,6dimethylphenyl isocyanide)cobalt(II), [CoBr 2 (C 9 H 9 N) 4 ] or trans-CoBr 2 (CNXyl) 4 , and trans-dibromidobis(2,6-dimethylphenyl isocyanide)nickel(II), [NiBr 2 (C 9 H 9 N) 2 ] or trans-NiBr 2 (CNXyl) 2 , are presented. Additionally, crystals grown from a cold diethyl ether solution of zero-valent Fe(CNXyl) 5 produced a structure containing a cocrystallization of mononuclear Fe(CNXyl) 5 and the previously unknown dinuclear [Fe(CNXyl) 3 ] 2 ( 2 -CNXyl) 3 , namely pentakis(2,6-dimethylphenyl isocyanide)iron(0) tris( 2 -2,6-dimethylphenyl isocyanide)bis[tris(2,6dimethylphenyl isocyanide)iron(0)], [Fe(C 9 H 9 N) 5 ][Fe 2 (C 9 H 9 N) 9 ]. The (M)C-N-C(Xyl) angles of the isocyanide ligand are nearly linear for the metals in the +2 oxidation state, for which the ligands function essentially as pure donors. The CN stretching frequencies for these divalent metal isocyanides are at or above that of the free ligand. Relative to Fe II , in the structure containing iron in the formally zero-valent oxidation state, the Fe-C bond lengths have shortened, the C N bond lengths have elongated, the (M)C-N-C(Xyl) angles of the terminal CNXyl ligands are more bent, and the CN stretching frequencies have shifted to lower energies, all indicative of substantial M(d)!* backbonding. research papers Acta Cryst. (2019). C75, 1118-1127 Brennessel et al. Fe/Co/Ni complexes of 2,6-dimethylphenyl isocyanide 1119 2. RefinementCrystal data, data collection and structure refinement details are summarized in Table 1. In 1, the cocrystallized dichloromethane solvent was modeled as disordered over a crystallographic twofold axis (0.50:0.50), and additionally over two general positions [0.593 (9) and 0.192 (9)]. The occupancies of the general positions were not required to sum to unity because it had been determined that there had been solvent loss during the mounting procedure. This loss was confirmed by a significant increase in R1 (strong data) when the occupancies were forced to sum to unity, as well as by examining the results of the SQUEEZE (Spek, 2015) routine of PLATON (Spek, 2009), which showed 150 electrons versus the expected 168. Analogous bond lengths and angles between the two positions of the dichloromethane solvent disorder were restrained to be similar. Anisotropic displacement parameters for proximal (including symmetry-equivalent) atoms were constrained to be equivalent. Additionally, anisotropic displacement parameters for all atoms of the major component were restrained to be similar.Methyl H atoms on C17 in 2a, C8, C9, and C17 in 2b, and C9 in 4 were modeled as rotationally disordered. research papers 1120 Brennessel et al....

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“…A certain resemblance to the “buckled dimer” of the reconstructed Si(100) surface is obvious for an amido-substituted Si 6 R 4 derivative, although the recently reported Si 9 R 3 – and Si 9 R 2 2– derivatives obviously feature even more “naked” vertices some of which are adjacent to one another. In neither of these cases, however, surface-like reactivity has been reported yet and a real functional model for the “buckled dimer” is still elusive despite the undoubted relevance of molecular disilenes and their reactivity for the Si(100) surface chemistry. − …”

Section: Discussionmentioning

confidence: 99%

Molecular Silicon Clusters

Heider

Scheschkewitz

2021

Chem. Rev.

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The continuously decreasing size of device features in microelectronics draws growing attention to the structuring of silicon at the molecular level with powerful tools provided by synthetic chemistry. Silicon clusters are of particular importance in this regard not only as potential precursors for silicon deposition but also as well-defined model systems for bulk and surfaces of silicon at the nanoscale as well as possible starting points for future construction of molecularly precise device structures. This review aims to give a comprehensive overview about the state of the art in the synthesis of molecular silicon clusters, which are grouped into (1) electron-precise saturated clusters, (2) soluble polyhedral Zintl anions, and (3) unsaturated silicon clusters, the so-called siliconoids. Particular attention is paid to functionalization as it is generally considered a necessary prerequisite for the design and construction of more extended systems. The interrelations between the three different classes of molecular silicon clusters, e.g., arising from the introduction of negatively charged functional groups, are highlighted on grounds of NMR properties and computed electronic structures.

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The Diverse Reactivity of Disilenes Toward Isocyanides

Cited by 6 publications

References 34 publications

Coordination Chemistry of Main Group Metals with Organic Isocyanides

Coordination Chemistry of Main Group Metals with Organic Isocyanides

Crystal structures and spectroscopic characterization of MBr₂(CNXyl)_n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)₅ and Fe₂(CNXyl)₉

Molecular Silicon Clusters

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The Diverse Reactivity of Disilenes Toward Isocyanides

Cited by 6 publications

References 34 publications

Coordination Chemistry of Main Group Metals with Organic Isocyanides

Coordination Chemistry of Main Group Metals with Organic Isocyanides

Crystal structures and spectroscopic characterization of MBr2(CNXyl) n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)5 and Fe2(CNXyl)9

Molecular Silicon Clusters

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Crystal structures and spectroscopic characterization of MBr₂(CNXyl)_n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)₅ and Fe₂(CNXyl)₉