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Journal articles on the topic 'Silicon-Ligand Bond'

Author: Grafiati

Published: 5 June 2025

Last updated: 1 August 2025

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1

MUSLIM, A. MOHAMMED, and URCH DAVID. "X-Ray Spectral Investigation of Silicon-Ligand Bond in Si(OC2H5)4, Si(C6H5)4 and (OH)2Si(C6H5)2 Compounds." Journal of Indian Chemical Society Vol. 74, Mar 1997 (1997): 174–75. https://doi.org/10.5281/zenodo.5876797.

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UMS, Kota Kinabalu, Sabah, Malaysia Chemistry Department, Queen-Mary & Westfield Collage, University of London, England <em>Manuscript received 5 May 1995, accepted 20 November 1995</em> X-Ray photoelectron and X-ray emission spectra (SiK<sub>α1,2</sub> and SiK<sub>β1,3</sub>) of the titled silicon compounds are studied. These spectra reveal only a-bonding in case of Si(OC<sub>2</sub>H<sub>5</sub>)<sub>4</sub> between silicon and ligand, but in case of Si(C<sub>6</sub>H<sub>5</sub>)<sub>4</sub> and (OH)<sub>2</sub>Si(C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>, both σ- and &pi

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2

Mohri, Fumihito. "A new relation between bond valence and bond distance." Acta Crystallographica Section B Structural Science 56, no. 4 (2000): 626–38. http://dx.doi.org/10.1107/s0108768100005401.

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A new empirical relationship s = s 0(R 0 − λ)3/(R − λ)3 between bond distances and bond valences is proposed, where s is the bond valence for the bond distance R, s 0 is the reference bond valence for the reference system with the reference bond distance R 0 and λ is the sum of the cation radii of bonding atoms defined by Pauling. Since λ is the size of the inner electron region, R − λ represents the valence electron region between bonding atoms. The new relationship was derived based on the following three hypotheses. (i) The number of electrons (p) in the volumes of (R − λ)3 in a coordinatio

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3

Patel, Dipti, and Stephen T. Liddle. "f-Element-metal bond chemistry." Reviews in Inorganic Chemistry 32, no. 1 (2012): 1–22. http://dx.doi.org/10.1515/revic.2012.0001.

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AbstractCompared to the overwhelming prevalence of f-element-carbon, -nitrogen, -oxygen or -halide ligand linkages, the use of metal-based fragments as ligands is underdeveloped. This contrasts directly to the extensively developed fields of d- and p-block metal-metal complexes, which are still burgeoning. This review outlines the development of compounds that possess polarised covalent f-element-metal bonds. For this review, the f-element is defined as (i) a group 3 metal; (ii) a lanthanide metal; (iii) the actinide metals thorium or uranium. The metal is defined as: (i) a d-block transition

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4

Gerlach, Daniela, Andreas W. Ehlers, Koop Lammertsma, and Jörg Wagler. "Silicon(IV) Chelates of an (ONN')-Tridentate Pyrrole-2-Carbaldimine Ligand: Syntheses, Structures and UV/Vis Properties." Zeitschrift für Naturforschung B 64, no. 11-12 (2009): 1571–79. http://dx.doi.org/10.1515/znb-2009-11-1242.

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The tridentate (ONN_)-chelator properties of the pyrrole-2-(o-hydroxyphenyl)carbaldimine dianion (L2−) were explored for the neutral penta-coordinate diorganosilicon complexes LSiRR' (R,R' = Ph, Ph; Ph, Me; Ph, tBu) where the ligand L occupies the ax-eq-ax sites in a distorted trigonalbipyramidal arrangement arround the silicon atom, and for the neutral hexa-coordinate L2Si, that has a mer-coordination. Single-crystal X-ray diffraction analyses show an almost planar ligand backbone with a Si-N bond to the imine group that is shorter in hexa-coordinate L2Si than in pentacoordinate LSiRR'. In sh

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5

Böhme, Uwe, Anke Schwarzer, and Betty Günther. "Formation of a macrocycle from dichlorodimethylsilane and a pyridoxalimine Schiff base ligand." Acta Crystallographica Section E Crystallographic Communications 77, no. 11 (2021): 1099–102. http://dx.doi.org/10.1107/s2056989021010185.

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The reaction of dichlorodimethylsilane with a polydentate Schiff base ligand derived from pyridoxal and 2-ethanolamine yielded the macrocyclic silicon compound (8E,22E)-4,4,12,18,18,26-hexamethyl-3,5,17,19-tetraoxa-8,13,22,27-tetraaza-4,18-disilatricyclo[22.4.0.010,15]octacosa-1(24),8,10,12,14,22,25,27-octaene-11,25-diol, C24H36N4O6Si2. The asymmetric unit contains the half macrocycle with an intramolecular O—H...N hydrogen bond between the imine nitrogen atom and a neighbouring oxygen atom. The crystal structure is dominated by C—H...O and C—H...π interactions, which form a high ordered molec

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6

Longo, Roberto C., Eric C. Mattson, Abraham Vega, et al. "Atomic Mechanism of Arsenic Monolayer Doping on oxide-free Silicon(111)." MRS Advances 1, no. 33 (2016): 2345–53. http://dx.doi.org/10.1557/adv.2016.466.

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AbstractThe reaction pathway for shallow arsenic doping of silicon by methylarsenic acid molecules directly grafted on oxide-free, H-terminated Si(111) surfaces is unraveled combining Infrared absorption spectroscopy, X-ray Photoelectron Spectroscopy, Low Energy Ion Scattering and ab initio Molecular Dynamics simulations. The overall driving force is identified as a thermodynamic instability of As+5 in contact with silicon, which initiates a self-decomposition of chemisorbed methylarsenic molecules at ∼600 K. As the temperature is increased, the As-C bond breaks -- the weakest link of the adso

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7

MacKay, Bruce A., Samuel A. Johnson, Brian O. Patrick, and Michael D. Fryzuk. "Functionalization and cleavage of coordinated dinitrogen via hydroboration using primary and secondary boranes." Canadian Journal of Chemistry 83, no. 4 (2005): 315–23. http://dx.doi.org/10.1139/v04-161.

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The reaction of the side-on, end-on ditantalum dinitrogen complex ([NPN]Ta)2(µ-η1:η2-N2)(µ-H)2 (where NPN = PhP(CH2SiMe2NPh)2) with a variety of secondary and primary boranes is reported. With 9-BBN, hydroboration of the Ta2N2 unit occurs via B-H addition, which in turn triggers a cascade of reactions that result in NN bond cleavage, ancillary ligand rearrangement involving silicon group migration, and finally elimination of benzene from the N-Ph group and a B-H moiety to generate the imidenitride derivative. In the presence of excess 9-BBN, the Lewis acid base adduct of the imidenitride

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8

Chairunisa, Ully, Indra Makmur, Rinna Desni Yetti та Aried Eriadi. "Molecular in Silico Test of the Interaction Between Keloid Cell Protein TGF – β1 (PDB ID: 3TZM) and Lycopene Compounds". International Journal of Research Publication and Reviews 03, № 12 (2022): 1342–48. http://dx.doi.org/10.55248/gengpi.2022.31237.

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Keloids are pathological scars, characterized histologically by excessive aggregation of type I collagen and fibroblasts in the reticular dermis inflammation. Scar tissue (keloid) is one problem the most frustrating in wound healing. Clinically, keloids are defined as a scar that invades adjacent healthy tissue and seldom experience regression along time. Keloids can be said to be a disorder of the healing wound, which form growth excessive from network scar, exceed limit wound, and beyond the normal time (can be years) wound healing process. In this research conducted development drug anti -

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9

Deis, Thomas, Jérémy Forte, Louis Fensterbank, and Gilles Lemière. "Synthesis and Reactivity of Martin’s Spirosilane-Derived Chloromethylsilicate." Molecules 27, no. 6 (2022): 1767. http://dx.doi.org/10.3390/molecules27061767.

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Pentacoordinate silicon derivatives with a chloromethyl ligand are versatile compounds that are usually obtained from the corresponding tetravalent trialkoxy- or trihalogeno(chloromethyl)silane. We describe herein the synthesis of a chloromethylsilicate bearing two Martin’s ligands readily obtained by addition of in situ generated chloromethyllithium to a spirosilane. The reactivity of this new species was evaluated and it has been established that the chloride is displaced by strong nucleophiles such as alkyllithiums and (hetero)aryllithiums. In Lewis acidic conditions, the pentacoordinate si

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10

Westerhausen, Matthias, and Wolfgang Schwarz. "Calcium-bis[N,N'-bis(trimethylsilyl)benzamidinat]-THF (1/2) - Synthese, spektroskopische Charakterisierung und Struktur/Calcium-bis[N,N'-bis(trimethylsilyl)benzamidinate]-THF (1/2) - Syntheses, Spectroscopic Characterization and Structure." Zeitschrift für Naturforschung B 47, no. 4 (1992): 453–59. http://dx.doi.org/10.1515/znb-1992-0401.

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The reaction of calcium-bis[bis(trimethylsilyl)amide]-THF (1/2) with benzonitrile in THF nearly quantitatively yields the title compound calcium-bis[N,N'-bis(trimethylsilyl)- benzamidinate]-THF (1/2). Under similar conditions pivalonitrile substitutes an ether ligand of calcium-bis[bis(trimethylsilyl)amide]-DME (1/2) without the formation of the corresponding amidinate derivative. The calcium-di(benzamidinate) [H5C6-C(NSiMe3)2]2Ca · 2THF crystallizes in the space group Pbcn with {a = 188.8(6); b = 1286.0(3); c = 1802.5(5) pm; Z = 4}. The calcium atom is hexa-coordinate with a distorted octahed

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11

Wang, Xu, Shuai-Shuai Huang, Feng-Jiao Zhang, et al. "Multifunctional P-ligand-controlled “silicon-centered” selectivity in Rh/Cu-catalyzed Si–C bond cleavage of silacyclobutanes." Organic Chemistry Frontiers 8, no. 23 (2021): 6577–84. http://dx.doi.org/10.1039/d1qo01386f.

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A newly developed Ar-BINMOL-Phos-controlled Rh/Cu-catalyzed (4+2) annulation of silacylcobutanes with arylpropiolate-type internal alkynes gave silicon-stereogenic 1-sila-2-cyclohexene derivatives with good ee and excellent chemoselectivity.

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12

Wang, Xu, Shuai-Shuai Huang, Feng-Jiao Zhang, et al. "Multifunctional P-ligand-controlled “silicon-centered” selectivity in Rh/Cu-catalyzed Si–C bond cleavage of silacyclobutanes." Organic Chemistry Frontiers 8, no. 23 (2021): 6577–84. http://dx.doi.org/10.1039/d1qo01386f.

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A newly developed Ar-BINMOL-Phos-controlled Rh/Cu-catalyzed (4+2) annulation of silacylcobutanes with arylpropiolate-type internal alkynes gave silicon-stereogenic 1-sila-2-cyclohexene derivatives with good ee and excellent chemoselectivity.

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13

Wagler, Jörg. "A Disilane with a Hypercoordinate Silicon Atom: Coordination of an Imine Ligand versus Si−Si Bond Splitting." Organometallics 26, no. 1 (2007): 155–59. http://dx.doi.org/10.1021/om060698a.

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14

Safa, Muhieddine, Michael C. Jennings, and Richard J. Puddephatt. "Reactivity of a Dimethylplatinum(II) Complex with the Bis(2-pyridyl)dimethylsilane Ligand: Easy Silicon–Carbon Bond Activation." Organometallics 31, no. 9 (2012): 3539–50. http://dx.doi.org/10.1021/om3000136.

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15

Forbes, Jeffrey G., and John P. Santos. "Solvent Isotope Effects in Atomic Force Spectroscopy." Microscopy and Microanalysis 7, S2 (2001): 856–57. http://dx.doi.org/10.1017/s143192760003035x.

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The utility of the atomic force microscope (AFM) for measuring forces is now well established. The AFM is capable of measuring forces from tens of piconewtons to tens of nanonewtons. Systems ranging from the adhesion of clean or functionalized tips interacting with different surface, to singlemolecule measurements of the force required to rupture protein-ligand interactions, to the forced unfolding of single protein molecules have been studied. The adhesion of a clean silicon nitride tip to a clean glass surface is one of the simplest systems to study and was the first system to demonstrate qu

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16

Robertson, Alasdair P. M., Saurabh S. Chitnis, Seth Chhina, et al. "Complexes of trimethylsilyl trifluoromethanesulfonate with nitrogen, oxygen, and phosphorus donors." Canadian Journal of Chemistry 94, no. 4 (2016): 424–29. http://dx.doi.org/10.1139/cjc-2015-0435.

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The Lewis acceptor chemistry of Me3SiOTf with p-block Lewis bases has been explored and a library of complexes has been characterized by spectroscopic and, where possible, crystallographic methods. Compounds with the generic formula [Me3Si(L)][OTf] (L = 4-dmap, pyr, imz, OPMe3, OPCy3, OPPh3, OpyrMe, dmso, PMe3) were isolated from 1:1 mixtures of Me3SiOTf and the respective ligand in CH2Cl2. Characterization by NMR spectroscopy confirmed the solution stability of all but [Me3Si(PMe3)][OTf], with indications that the latter dissociates into PMe3 and Me3SiOTf. Solid-state structures of [Me3Si(4-d

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17

Cammidge, Andrew N., Fabien Nekelson, David L. Hughes, Zhixin Zhao та Michael J. Cook. "Stepwise syntheses of complex μ-oxo-linked heterochromophore arrays containing phthalocyanine, porphyrin and subphthalocyanine ligands". Journal of Porphyrins and Phthalocyanines 14, № 12 (2010): 1001–11. http://dx.doi.org/10.1142/s1088424610002926.

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The article reviews the exploitation of the serendipitous discovery that dihydroxysilicon 1,4,8,11,15,18,22,25-octakis(hexyl)phthalocyanine 1 reacts at one face only to form a μ-oxo linked bond to dichlorosilicon phthalocyanine. Reaction of 1 with dihydroxysilicon octaethylporphyrin led to an unstable μ-oxo linked Pc-O-Pn heteroligand dyad that could not be isolated. However, reaction with dihydroxygermanium octaethylporphyrin gave a stable dyad that showed substantial broad band absorption attributable to exciton effects. A small amount of the μ-oxo linked homo dyad formed by self-condensatio

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18

Djurovich, Peter I., and Richard J. Watts. "Excited states of nitrogen, silicon-chelated transition metal complexes: characteristics of .sigma.-bond-to-ligand charge-transfer (SBLCT) excited states in fac-Ir[(6-isopropyl-8-quinolyl)diorganosilyl]3." Inorganic Chemistry 32, no. 22 (1993): 4681–82. http://dx.doi.org/10.1021/ic00074a006.

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19

Passarelli, Vincenzo, Giovanni Carta, Gilberto Rossetto, and Pierino Zanella. "Aminolysis of the Si–Cl bond and ligand exchange reaction between silicon amido derivatives and SiCl4: synthetic applications and kinetic investigationsElectronic supplementary information (ESI) available: details of the aminolysis and the ligand exchange reaction. See http://www.rsc.org/suppdata/dt/b2/b210282j/." Dalton Transactions, no. 3 (January 8, 2003): 413–19. http://dx.doi.org/10.1039/b210282j.

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20

Meltzer, Antje, Shigeyoshi Inoue, Carsten Präsang, and Matthias Driess. "Steering S−H and N−H Bond Activation by a Stable N-Heterocyclic Silylene: Different Addition of H2S, NH3, and Organoamines on a Silicon(II) Ligand versus Its Si(II)→Ni(CO)3Complex." Journal of the American Chemical Society 132, no. 9 (2010): 3038–46. http://dx.doi.org/10.1021/ja910305p.

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21

Tanaka, Takayuki, and Atsuhiro Osuka. "Tetracoordinate silicon complexes of 1,2-bis(indol-2-yl)benzene as blue-emitting dyes in the solid state." Chemical Communications 51, no. 38 (2015): 8123–25. http://dx.doi.org/10.1039/c5cc01625h.

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22

Abhi Purwoko, Agus, Saprizal Hadisaputra, and Alistair J. Less. "Experimental and Theoretical Study of the Silicon-Hydrogen Bond Activation by Rhodium Dicarbonyl Complex in Solution." Journal of the Indonesian Chemical Society 2, no. 2 (2019): 121. http://dx.doi.org/10.34311/jics.2019.02.2.121.

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The photoreactivity of hydrotris-(3,5-dimethylpyrazolyl)boratedicarbonylrhodium(I) or HB(Pz*)3Rh(CO)2 complex has been studied at room-temperature n-pentane solution in the presence of 0.05 M Et3SiH (Et = C2H5). The IR spectra show that the decline of νCO parent complex at 1980 and 2054 cm-1 is followed by growing bands at 2029 and 2020 cm-1. In light of the photolysis of the parent complex in neat n-pentane solution the feature at 2020 cm-1 is tentatively assigned to the νCO band of the Si-H bond activation product. Upon standing in the dark, the 2020 cm-1 increases slightly in contrast with

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23

Wagler, Jörg, Uwe Böhme, Erica Brendler, and Gerhard Roewer. "First X-Ray Structure of a Cationic Silicon Complex with Salen-Type Ligand: An Unusual Compound with Two Different Si-N Dative Bonds." Zeitschrift für Naturforschung B 59, no. 11-12 (2004): 1348–52. http://dx.doi.org/10.1515/znb-2004-11-1255.

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Abstract Two novel compounds containing pentacoordinate alkylsiliconium-cations with an 〈O, N, O 〉- chelating ligand of salen-type were prepared by reacting the trimethylsilyl derivatives of the ligand with alkyltrichlorosilanes. Pentacoordination of the silicon atom is found in solid state as well as in solution. Crystals of compound 2a, ethylene-N, N’ -bis(2-oxy-4-methoxybenzophenoneiminato) methylsiliconium chloride, were obtained from chloroform solution. This complex crystallizes in monoclinic space group P21/n. The chloride ion is surrounded by three chloroform molecules in the solid sta

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24

Auner, Norbert, Reiner Probst, Claus-Rüdiger Heikenwälder, Eberhardt Herdtweck, Siegfried Gamper, and Gerhard Müller. "Beeinflussen interne N-Donorliganden Hydrolyse-und Kondensationsreaktionen von Chlorsilanen? / Do Internal N-Donor Ligands Influence the Hydrolysis and Condensation Reactions of Chlorosilanes?" Zeitschrift für Naturforschung B 48, no. 11 (1993): 1625–34. http://dx.doi.org/10.1515/znb-1993-1123.

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The reaction of [C6H4CH2N(CH3)2]2SiCl2 (1) with hydrogen chloride gives the singly protonated adduct 2. Its solid state structure has been determined by single crystal X-ray diffraction. Centrosymmetric 2 is orthorhombic, space group Pbca, a = 1694.9(2), b = 1161.7(2), c = 2501.7(3) pm; Z = 8. Controlled hydrolysis of 1 leads to the 1,3-siloxanediol 4, probably via the precursors 3a-3c which could not be isolated. The hydrogen chloride formed during the hydrolysis protonates two of the dimethylamino groups, while the other two dimethylamino functions form hydrogen bonds to the silanol groups.

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25

Huang, Deqiu, Fujian Zhao, Wendong Gao, Xiaofeng Chen, Zhouyi Guo, and Wen Zhang. "Strontium-substituted sub-micron bioactive glasses inhibit ostoclastogenesis through suppression of RANKL-induced signaling pathway." Regenerative Biomaterials 7, no. 3 (2020): 303–11. http://dx.doi.org/10.1093/rb/rbaa004.

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Abstract Strontium-substituted bioactive glass (Sr-BG) has shown superior performance in bone regeneration. Sr-BG-induced osteogenesis has been extensively studied; however, Sr-BG-mediated osteoclastogenesis and the underlying molecular mechanism remain unclear. It is recognized that the balance of osteogenesis and osteoclastogenesis is closely related to bone repair, and the receptor activators of nuclear factor kappaB ligand (RANKL) signaling pathway plays a key role of in the regulation of osteoclastogenesis. Herein, we studied the potential impact and underling mechanism of strontium-subst

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26

Fielding, Gary A., Naboneeta Sarkar, Sahar Vahabzadeh, and Susmita Bose. "Regulation of Osteogenic Markers at Late Stage of Osteoblast Differentiation in Silicon and Zinc Doped Porous TCP." Journal of Functional Biomaterials 10, no. 4 (2019): 48. http://dx.doi.org/10.3390/jfb10040048.

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Calcium phosphates (CaPs) are one of the most widely used synthetic materials for bone grafting applications in the orthopedic industry. Recent trends in synthetic bone graft applications have shifted towards the incorporation of metal trace elements that extend the performance of CaPs to have osteoinductive properties. The objective of this study is to investigate the effects of silicon (Si) and zinc (Zn) dopants in highly porous tricalcium phosphate (TCP) scaffolds on late-stage osteoblast cell differentiation markers. In this study, an oil emulsion method is utilized to fabricate highly por

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27

Junold, Konstantin, Johannes A. Baus, Christian Burschka, Thomas Vent-Schmidt, Sebastian Riedel, and Reinhold Tacke. "Five-Coordinate Silicon(II) Compounds with Si–M Bonds (M = Cr, Mo, W, Fe): Bis[N,N′-diisopropylbenzamidinato(−)]silicon(II) as a Ligand in Transition-Metal Complexes." Inorganic Chemistry 52, no. 19 (2013): 11593–99. http://dx.doi.org/10.1021/ic401954e.

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28

Azami, Niloufar, Po-Jung Chen, Shivam Mehta, et al. "Raloxifene administration enhances retention in an orthodontic relapse model." European Journal of Orthodontics 42, no. 4 (2020): 371–77. http://dx.doi.org/10.1093/ejo/cjaa008.

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Abstract Background and objectives Orthodontic relapse is a physiologic process that involves remodelling of the alveolar bone and principle periodontal ligament fibres. Raloxifene is an Food and Drug Administration (FDA)-approved selective oestrogen receptor modulator that inhibits systemic bone loss. In our study, we examined the effects of Raloxifene on alveolar bone modelling and orthodontic relapse in a rodent model. Materials and methods The efficacy of raloxifene was evaluated in 15-week-old male Wistar rats, 8 in each group (Control, Raloxifene, Raloxifene + 7-day relapse, Raloxifene +

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Chae, Wook-Jin, Theingi Aung, Sujeong Song, and Hisashi Harada. "Abstract LB384: Dickkopf1(DKK1) is a novel endogenous priming ligand for NLRP3 inflammasome activation in macrophages to promote cancer." Cancer Research 85, no. 8_Supplement_2 (2025): LB384. https://doi.org/10.1158/1538-7445.am2025-lb384.

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Abstract Dickkopf1 (DKK1) is a quintessential Wnt antagonist and has gained significant attention recently with its multifaceted role in modulating immune responses. Elevated levels of DKK1 in multiple cancer types such as gastric, breast, and head and neck cancer underscores its significance as a potential biomarker and therapeutic target for cancer immunotherapy. However, the underlying molecular mechanisms of DKK1’s role in inflammatory diseases remain unclear. Here, we demonstrated that DKK1 acts as an endogenous priming ligand for NLRP3 (NOD-, LRR- and pyrin domain-containing protein 3) i

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Dhara, Arpan, Aditya Chalishazar, Jolien Dendooven, and Christophe Detavernier. "Molecular Layer Deposition of Metal Phosphonates: A New Class of Hybrid Coating Layers." ECS Meeting Abstracts MA2023-02, no. 29 (2023): 1493. http://dx.doi.org/10.1149/ma2023-02291493mtgabs.

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Atomic layer deposition (ALD) is a vapor phase thin film deposition technique where materials can be grown atom-by-atom in a layer-by-layer manner. Over the course of just few years, it has become to be one of the most sophisticated methods of producing high quality thin films with control at the sub-nanometer scale. Molecular layer deposition (MLD) is a variant of ALD where molecular fragments are intentionally built into the growing films. MLD is one of the techniques which allows to grow organic-inorganic hybrid materials with thickness control at sub-nanometer level.1 Nowadays, organic-ino

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Zong, Hongliang, Siddhartha Sen, Guodong Zhang, et al. "Novel Multistage Nanoparticle Drug Delivery to Ablate Leukemia Stem Cells in Their Niche." Blood 120, no. 21 (2012): 2631. http://dx.doi.org/10.1182/blood.v120.21.2631.2631.

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Abstract Abstract 2631 Most patients with acute myelogenous leukemia (AML) die from their disease. Although up to 75% of AML patients achieve remission after initial induction therapy, most of them will relapse and it has been proposed that relapse is the result of ineffective ablation of leukemia stem cells (LSCs) by chemotherapy. Elevated levels of phenotypically defined LSCs at diagnosis are predictive of minimal residual disease (MRD) which, in turn, predicts leukemic relapse, even after myeloablative stem cell transplantation. Therefore, in order to improve AML therapy, it is imperative t

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32

Shang, Wen-Jing, Qi Zhou, Jia-Wei Si, et al. "Palladium‐Catalyzed Ring Expansion of Benzosilacyclobutenes: Ligand Substituent Effects on Stereodivergent Catalysis." Asian Journal of Organic Chemistry, March 28, 2025. https://doi.org/10.1002/ajoc.202500169.

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Transition‐metal‐catalyzed silicon‐carbon bond activation of small silacycles has proven particularly useful in direct synthesis of silicon‐containing heterocycles. Despite significant advances in the synthesis of new silacycles based on Si‐C bond activation of silacyclobutanes, a fascinating challenge lies in the construction of silicon‐stereogenic benzosilacycles from the ring expansion of racemic benzosilacyclobutenes. Herein, we present an example of palladium‐catalyzed asymmetric Si‐C bond activation of racemic benzosilacyclobutenes and its ring expansion with conjugated alkynes to addres

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33

Mo, Zhenbo, Jinghuang Lv, Xiao Fang, and Fanshu Cao. "Cooperative Activation of CO and Pyridine by an Aluminum(I) Complex Ligated with a Silylene‐Borane Ligand." Angewandte Chemie, July 8, 2025. https://doi.org/10.1002/ange.202512084.

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Cooperative main‐group systems based on alumylenes are highly attractive due to their potential for activating and transforming inert chemical bonds and small molecules. However, their development has been hindered by the scarcity of suitable supporting ligands. Herein, we report the synthesis of an amphiphilic carboranyl silylene‐borane ligand (1) and demonstrate its effectiveness in stabilizing an aluminum(I) complex 2. Complex 2 has been unambiguously characterized by spectroscopic analysis, X‐ray diffraction analysis and DFT calculations, which reveals a unique structure featuring both sil

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34

Mo, Zhenbo, Jinghuang Lv, Xiao Fang, and Fanshu Cao. "Cooperative Activation of CO and Pyridine by an Aluminum(I) Complex Ligated with a Silylene‐Borane Ligand." Angewandte Chemie International Edition, July 8, 2025. https://doi.org/10.1002/anie.202512084.

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Cooperative main‐group systems based on alumylenes are highly attractive due to their potential for activating and transforming inert chemical bonds and small molecules. However, their development has been hindered by the scarcity of suitable supporting ligands. Herein, we report the synthesis of an amphiphilic carboranyl silylene‐borane ligand (1) and demonstrate its effectiveness in stabilizing an aluminum(I) complex 2. Complex 2 has been unambiguously characterized by spectroscopic analysis, X‐ray diffraction analysis and DFT calculations, which reveals a unique structure featuring both sil

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35

Dodonov, Vladimir Alekseevich, Alina A. Kryuchenkova, Olga A. Kushnerova, et al. "Cooperative and Non-Cooperative Additions Involving Silicon Atom and Redox-active Ligand." Dalton Transactions, 2025. https://doi.org/10.1039/d4dt03409k.

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The silylene [(dpp-bian)Si:] (1), where dpp-bian is 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene, exhibits remarkable reactivity with a variety of substrates. It reacts with chloroform and water via O–H and C–Cl bond activation to yield...

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Wenzel, Jonas O., Johannes Werner, and Frank Breher. "Non‐Innocent Ligands as Mediators for Visible‐Light‐Initiated Element – Carbon Bond Homolysis in Main Group Chemistry." Angewandte Chemie, May 14, 2025. https://doi.org/10.1002/ange.202507060.

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Photoinitiated homolysis of element‐carbon bonds is an important method for the generation of carbon‐centered radicals in catalysis and organometallic or polymer chemistry. In this respect, the use of earth‐abundant main group elements such as aluminum or silicon is attractive. Generally, subvalent species derived from these typically redox‐inactive elements are unstable and within their high‐valent configuration +III (Al) or +IV (Si) comparatively strong E–C bonds are formed. Therefore, E–C homolysis usually requires short‐wave UV irradiation, which hampers their use as radical sources. Some

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Wenzel, Jonas O., Johannes Werner, and Frank Breher. "Non‐Innocent Ligands as Mediators for Visible‐Light‐Initiated Element – Carbon Bond Homolysis in Main Group Chemistry." Angewandte Chemie International Edition, May 14, 2025. https://doi.org/10.1002/anie.202507060.

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Photoinitiated homolysis of element‐carbon bonds is an important method for the generation of carbon‐centered radicals in catalysis and organometallic or polymer chemistry. In this respect, the use of earth‐abundant main group elements such as aluminum or silicon is attractive. Generally, subvalent species derived from these typically redox‐inactive elements are unstable and within their high‐valent configuration +III (Al) or +IV (Si) comparatively strong E–C bonds are formed. Therefore, E–C homolysis usually requires short‐wave UV irradiation, which hampers their use as radical sources. Some

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38

Greb, Lutz. "p-Block Element Catecholates: Lewis Superacidic, Constitutionally Dynamic and Redox-Active." Synlett, July 4, 2023. http://dx.doi.org/10.1055/a-2122-8238.

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Numerous strategies for enhancing the reactivity and properties of p-block elements have been devised in the past decades. The present Account article discusses our approaches by a distinct ligand control on p-block elements in their normal (group) oxidation states. Catecholato ligands at silicon, germanium, and phosphorous enable a range of rewarding properties. Substantial electron withdrawal paired with structural constraint effects (influence of deformation energy) impart Lewis superacidity to these abundant elements. The ease of synthesis of such species facilitates screening in catalysis

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McGill, R. Andrew, Duane Simonson, Julie H. Ta, et al. "Solutochromic Molecular Spectroscopy with a Reference Hydrogen-Bond Acid Dendrimer." MRS Proceedings 1403 (2012). http://dx.doi.org/10.1557/opl.2012.776.

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A zeroth order dendritic carbosilane structure, SiFA4H with four hexafluoroisopropanol (HFIP) functional groups attached via propyl ligand arms to a central silicon atom, has been developed as a model hydrogen-bond (HB) acid sorbent coating and candidate reference HB acid. The HB donor interaction, through the hydroxyl of the HFIP moiety, with a solute HB base can be monitored by observing the hydroxyl stretching frequency through measurements of SiFA4H FTIR spectra before and during vapor exposure. HFIP hydroxyl stretch shifts, upwards of 700 cm-1 have been observed depending on the HB base.

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Chang, Shun-Qin, Yueping Lin, Pei Gu, Changhui Lu, Minyan Wang, and Liangbin Huang. "Ligand-Controlled Nickel-Catalyzed C−O Bond Cleavage of SilylEnol Ether for the Divergent Synthesis of Aryl Alkenes and Silicon-Containing Product." Organic Chemistry Frontiers, 2025. http://dx.doi.org/10.1039/d4qo01906g.

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Silyl enol ethers are easily prepared from available ketones, which are widely used as α-carbon nucleophiles in organic synthesis. It’s challenging to use this motif as electrophiles via the activation...

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41

Laglera-Gándara, Carlos, Julián Jiménez-Pérez, Francisco José Fernández-de-Córdova, Pablo Ríos, and Salvador Conejero. "Electrophilic Hydrosilylation of Electron‐Rich Alkenes Derived from Enamines." Angewandte Chemie, April 18, 2024. http://dx.doi.org/10.1002/ange.202404859.

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The low‐electron count, air‐stable, platinum complexes [Pt(ItBu’)(ItBu)][BArF] (C1) (ItBu=1,3‐di‐tert‐butylimidazol‐2‐ylidene), [Pt(SiPh)3(ItBuiPr)2][BArF] (C2) (ItBuiPr = 1‐tert‐butyl‐3‐iso‐propylimidazol‐2‐ylidene), [Pt(SiPh)3(ItBuMe)2][BArF] (C3), [Pt(GePh3)(ItBuiPr)2][BArF] (C4), [Pt(GePh)3(ItBuMe)2][BArF] (C5) and [Pt(GeEt)3(ItBuMe)2][BArF] (C6) (ItBuMe = 1‐tert‐butyl‐3‐methylimidazol‐2‐ylidene) are efficient catalysts (particularly the germyl derivatives) in both the silylative dehydrocoupling and hydrosilylation of electron rich alkenes derived from enamines. The steric hindrance exerte

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42

Laglera-Gándara, Carlos, Julián Jiménez-Pérez, Francisco José Fernández-de-Córdova, Pablo Ríos, and Salvador Conejero. "Electrophilic Hydrosilylation of Electron‐Rich Alkenes Derived from Enamines." Angewandte Chemie International Edition, April 18, 2024. http://dx.doi.org/10.1002/anie.202404859.

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The low‐electron count, air‐stable, platinum complexes [Pt(ItBu’)(ItBu)][BArF] (C1) (ItBu=1,3‐di‐tert‐butylimidazol‐2‐ylidene), [Pt(SiPh)3(ItBuiPr)2][BArF] (C2) (ItBuiPr = 1‐tert‐butyl‐3‐iso‐propylimidazol‐2‐ylidene), [Pt(SiPh)3(ItBuMe)2][BArF] (C3), [Pt(GePh3)(ItBuiPr)2][BArF] (C4), [Pt(GePh)3(ItBuMe)2][BArF] (C5) and [Pt(GeEt)3(ItBuMe)2][BArF] (C6) (ItBuMe = 1‐tert‐butyl‐3‐methylimidazol‐2‐ylidene) are efficient catalysts (particularly the germyl derivatives) in both the silylative dehydrocoupling and hydrosilylation of electron rich alkenes derived from enamines. The steric hindrance exerte

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43

De, Siddhartha, Arpan Mondal, Sean Giblin, and Richard Layfield. "Bimetallic Synergy Enables Silole Insertion into THF and the Synthesis of Erbium Single‐Molecule Magnets." Angewandte Chemie International Edition, February 2024. http://dx.doi.org/10.1002/anie.202317678.

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The potassium silole K2[SiC4‐2,5‐(SiMe3)2‐3,4‐Ph2] reacts with [M(η8‐COT)(THF)4][BPh4] (M = Er, Y; COT = cyclo‐octatetraenyl) in THF to give products that feature unprecedented insertion of the nucleophilic silicon centre into a carbon‐oxygen bond of THF. The structure of the major product, [(μ‐η8:η8‐COT)M(m‐L1)K][[EQUATION]] (1M), consists of polymeric chains of sandwich complexes, where the spiro‐bicyclic silapyran ligand [C4H8OSiC4(SiMe3)2Ph2]2– (L1) coordinates to potassium via the oxygen. The minor product [(μ‐η8:η8‐COT)M(m‐L1)K(THF)]2 (2M) features coordination of the silapyran to the ra

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De, Siddhartha, Arpan Mondal, Sean Giblin, and Richard Layfield. "Bimetallic Synergy Enables Silole Insertion into THF and the Synthesis of Erbium Single‐Molecule Magnets." Angewandte Chemie, February 2024. http://dx.doi.org/10.1002/ange.202317678.

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The potassium silole K2[SiC4‐2,5‐(SiMe3)2‐3,4‐Ph2] reacts with [M(η8‐COT)(THF)4][BPh4] (M = Er, Y; COT = cyclo‐octatetraenyl) in THF to give products that feature unprecedented insertion of the nucleophilic silicon centre into a carbon‐oxygen bond of THF. The structure of the major product, [(μ‐η8:η8‐COT)M(m‐L1)K][[EQUATION]] (1M), consists of polymeric chains of sandwich complexes, where the spiro‐bicyclic silapyran ligand [C4H8OSiC4(SiMe3)2Ph2]2– (L1) coordinates to potassium via the oxygen. The minor product [(μ‐η8:η8‐COT)M(m‐L1)K(THF)]2 (2M) features coordination of the silapyran to the ra

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45

Chang, Che-Chen, and Ing-Jye Huang. "The Decomposition of tBAA on the Silicon Surface." MRS Proceedings 672 (2001). http://dx.doi.org/10.1557/proc-672-o9.12.

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ABSTRACTAmong the copper precursors used, cupric β-diketonate complexes exhibit a high sublimationrate and a low pyrolysis temperature. This work explored the possibility of using a nonfluorinated t-butylacetato complex of Cu(II) as the precursor. Secondary ion mass spectrometry and temperature-program desorption studies on the adsorption and decomposition of the ligand, tert-butyl acetoacetate (tBAA), of this precursor on Si(100) showed that at low doses, all tBAA molecules dissociated readily upon adsorption on the surface at substrate temperatures as low as –160°C. For dissociation through

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46

Böhme, Uwe, and Sabine Fels. "{N-[1-(2-Oxidophenyl)ethylidene]-DL-alaninato}(pentane-1,5-diyl)silicon(IV)." IUCrData 9, no. 3 (2024). http://dx.doi.org/10.1107/s2414314624002281.

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The title SiIV complex, C16H21NO3Si, is built up by a tridentate dinegative Schiff base ligand bound to a silacyclohexane unit. The coordination geometry of the pentacoordinated SiIV atom is a distorted trigonal bipyramid. The presence of the silacyclohexane ring in the complex leads to an unusual coordination geometry of the SiIV atom with the N atom from the Schiff base ligand and an alkyl-C atom in apical positions of the trigonal bipyramid. There is a disorder of the methyl group at the imine bond with two orientations resolved for the H atoms [major orientation = 0.55 (3)]. In the crystal

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47

Huo, Jingfeng, Kangbao Zhong, Yazhen Xue, et al. "Ligand‐Controlled Site‐ and Enantioselective Carbene Insertion into Carbon‐Silicon Bonds of Benzosilacyclobutanes." Chemistry – A European Journal, April 2022. http://dx.doi.org/10.1002/chem.202200191.

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48

Wang, Jiahao, Liang Zhang, Lingjun Wang, et al. "Ligand‐Selective Targeting of Macrophage Hydrogel Elicits Bone Immune‐Stem Cell Endogenous Self‐Healing Program to Promote Bone Regeneration." Advanced Healthcare Materials, January 19, 2024. http://dx.doi.org/10.1002/adhm.202303851.

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AbstractTargeting macrophages can facilitate the site‐specific repair of critical bone defects. Herein, a composite hydrogel, gelatin‐Bletilla striata polysaccharide‐mesoporous bioactive glass hydrogel (GBMgel), is constructed via the self‐assembly of mesoporous bioactive glass on polysaccharide structures, through the Schiff base reaction. GBMgel can efficiently capture macrophages and drive the recruitment of seed stem cells and vascular budding required for regeneration in the early stages of bone injury, and the observed sustained release of inorganic silicon ions further enhances bone mat

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Liu, Xiaona, Yuyang Dai, Qidi Bao, et al. "Isolable T‐Shaped Planar Silyl Anion." Angewandte Chemie International Edition, May 23, 2024. http://dx.doi.org/10.1002/anie.202406089.

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Silyl anions have garnered significant attention due to their synthetic abilities. However, previously reported silyl anions have been limited to either trigonal‐pyramidal or trigonal‐planar geometries, which confine them primarily as nucleophiles in substitution reactions. Herein, we report the isolation of the unprecedented T‐shaped planar silyl anion salt 2 by employment of a geometrically constrained triamido pincer ligand. Theoretical calculations disclosed that the silicon centre in 2 possesses both a lone pair of electrons and an empty 3pz orbital. In addition to nucleophilic substituti

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50

Liu, Xiaona, Yuyang Dai, Qidi Bao, et al. "Isolable T‐Shaped Planar Silyl Anion." Angewandte Chemie, May 23, 2024. http://dx.doi.org/10.1002/ange.202406089.

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Silyl anions have garnered significant attention due to their synthetic abilities. However, previously reported silyl anions have been limited to either trigonal‐pyramidal or trigonal‐planar geometries, which confine them primarily as nucleophiles in substitution reactions. Herein, we report the isolation of the unprecedented T‐shaped planar silyl anion salt 2 by employment of a geometrically constrained triamido pincer ligand. Theoretical calculations disclosed that the silicon centre in 2 possesses both a lone pair of electrons and an empty 3pz orbital. In addition to nucleophilic substituti

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