Coordination Chemistry of Silicon Edited by Shigeyoshi Inoue Printed Edition of the Special Issue Published in Inorganics www.mdpi.com/journal/inorganics Coordination Chemistry of Silicon Coordination Chemistry of Silicon Special Issue Editor Shigeyoshi Inoue MDPI • Basel • Beijing • Wuhan • Barcelona • Belgrade Special Issue Editor Shigeyoshi Inoue Technische Universitat¨ Munchen¨ Germany Editorial Office MDPI St. Alban-Anlage 66 4052 Basel, Switzerland This is a reprint of articles from the Special Issue published online in the open access journal Inorganics (ISSN 2304-6740) from 2017 to 2019 (available at: https://www.mdpi.com/journal/inorganics/ special issues/coordination chemistryn) For citation purposes, cite each article independently as indicated on the article page online and as indicated below: LastName, A.A.; LastName, B.B.; LastName, C.C. Article Title. Journal Name Year, Article Number, Page Range. 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Contents About the Special Issue Editor ...................................... vii Shigeyoshi Inoue Coordination Chemistry of Silicon Reprinted from: Inorganics 2019, 7, 7, doi:10.3390/inorganics7010007 ................ 1 J¨urgen Kahr, Ferdinand Belaj and Rudolf Pietschnig Preparation and Molecular Structure of a Cyclopentyl-Substituted Cage Hexasilsesquioxane T6 (T = cyclopentyl-SiO1.5) Starting from the Corresponding Silanetriol Reprinted from: Inorganics 2017, 5, 66, doi:10.3390/inorganics5040066 ................ 5 Norio Nakata, Nanami Kato, Noriko Sekizawa and Akihiko Ishii Si–H Bond Activation of a Primary Silane with a Pt(0) Complex: Synthesis and Structures of Mononuclear (Hydrido)(dihydrosilyl) Platinum(II) Complexes Reprinted from: Inorganics 2017, 5, 72, doi:10.3390/inorganics5040072 ................ 13 Tomohiro Sugahara, Norihiro Tokitoh and Takahiro Sasamori Synthesis of a Dichlorodigermasilane: Double Si–Cl Activation by a Ge=Ge Unit Reprinted from: Inorganics 2017, 5, 79, doi:10.3390/inorganics5040079 ................ 24 Yusuke Sunada, Nobuhiro Taniyama, Kento Shimamoto, Soichiro Kyushin and Hideo Nagashima Construction of a Planar Tetrapalladium Cluster by the Reaction of Palladium(0) Bis(isocyanide) with Cyclic Tetrasilane Reprinted from: Inorganics 2017, 5, 84, doi:10.3390/inorganics5040084 ................ 32 Jonathan O. Bauer and Carsten Strohmann Molecular Structures of Enantiomerically-Pure (S)-2-(Triphenylsilyl)- and (S)-2-(Methyldiphenylsilyl)pyrrolidinium Salts Reprinted from: Inorganics 2017, 5, 88, doi:10.3390/inorganics5040088 ................ 44 Rabia Ayub, Kjell Jorner and Henrik Ottosson The Silacyclobutene Ring: An Indicator of Triplet State Baird-Aromaticity Reprinted from: Inorganics 2017, 5, 91, doi:10.3390/inorganics5040091 ................ 52 Yohei Adachi, Daiki Tanaka, Yousuke Ooyama and Joji Ohshita Modification of TiO2 Surface by Disilanylene Polymers and Application to Dye-Sensitized Solar Cells Reprinted from: Inorganics 2018, 6, 3, doi:10.3390/inorganics6010003 ................ 68 Debabrata Dhara, Volker Huch, David Scheschkewitz and Anukul Jana Synthesis of a α-Chlorosilyl Functionalized Donor-Stabilized Chlorogermylene Reprinted from: Inorganics 2018, 6, 6, doi:10.3390/inorganics6010006 ................ 78 Fabian Dankert, Kirsten Reuter, Carsten Donsbach and Carsten von H¨anisch Hybrid Disila-Crown Ethers as Hosts for Ammonium Cations: The O–Si–Si–O Linkage as an Acceptor for Hydrogen Bonding Reprinted from: Inorganics 2018, 6, 15, doi:10.3390/inorganics6010015 ................ 84 Lisa Pecher and Ralf Tonner Bond Insertion at Distorted Si(001) Subsurface Atoms Reprinted from: Inorganics 2018, 6, 17, doi:10.3390/inorganics6010017 ................ 94 v Naohiko Akasaka, Kaho Tanaka, Shintaro Ishida and Takeaki Iwamoto Synthesis and Functionalization of a 1,2-Bis(trimethylsilyl)-1,2-disilacyclohexene That Can Serve as a Unit of cis-1,2-Dialkyldisilene Reprinted from: Inorganics 2018, 6, 21, doi:10.3390/inorganics6010021 ................108 Naoki Hayakawa, Kazuya Sadamori, Shinsuke Mizutani, Tomohiro Agou, Tomohiro Sugahara, Takahiro Sasamori, Norihiro Tokitoh, Daisuke Hashizume and Tsukasa Matsuo Synthesis and Characterization of N-Heterocyclic Carbene-Coordinated Silicon Compounds Bearing a Fused-Ring Bulky Eind Group Reprinted from: Inorganics 2018, 6, 30, doi:10.3390/inorganics6010030 ................123 Laura-Alice Jantke and Thomas F. F¨assler 3 Predicted Siliconoids by Bridging Si9 Clusters through sp -Si Linkers Reprinted from: Inorganics 2018, 6, 31, doi:10.3390/inorganics6010031 ................134 Amelie Porzelt, Julia I. Schweizer, Ramona Baierl, Philipp J. Altmann, Max C. Holthausen and Shigeyoshi Inoue S–H Bond Activation in Hydrogen Sulfide by NHC-Stabilized Silyliumylidene Ions Reprinted from: Inorganics 2018, 6, 54, doi:10.3390/inorganics6020054 ................142 Ravindra K. Raut, Sheikh Farhan Amin, Padmini Sahoo, Vikas Kumar and Moumita Majumdar One-Pot Synthesis of Heavier Group 14 N-Heterocyclic Carbene Using Organosilicon Reductant Reprinted from: Inorganics 2018, 6, 69, doi:10.3390/inorganics6030069 ................156 Yasunobu Egawa, Chihiro Fukumoto, Koichiro Mikami, Nobuhiro Takeda and Masafumi Unno Synthesis and Characterization of the Germathioacid Chloride Coordinated by an N-Heterocyclic Carbene § Reprinted from: Inorganics 2018, 6, 76, doi:10.3390/inorganics6030076 ................162 Ken-ichiro Kanno, Yumi Aikawa, Yuka Niwayama, Misaki Ino, Kento Kawamura and Soichiro Kyushin Stepwise Introduction of Different Substituents to α-Chloro-ω-hydrooligosilanes: Convenient Synthesis of Unsymmetrically Substituted Oligosilanes Reprinted from: Inorganics 2018, 6, 99, doi:10.3390/inorganics6030099 ................170 Naohiko Akasaka, Shintaro Ishida and Takeaki Iwamoto Transformative Si8R8 Siliconoids Reprinted from: Inorganics 2018, 6, 107, doi:10.3390/inorganics6040107 ...............184 Lisa Ehrlich, Robert Gericke, Erica Brendler and J¨orgWagler (2-Pyridyloxy)silanes as Ligands in Transition Metal Coordination Chemistry Reprinted from: Inorganics 2018, 6, 119, doi:10.3390/inorganics6040119 ...............196 vi About the Special Issue Editor Shigeyoshi Inoue, Professor, Dr., studied at the University of Tsukuba and carried out his doctoral studies, obtaining his Ph.D. in 2008. As a Humboldt grantee as well as a JSPS grantee, he spent the academic year 2008–2010 at the Technische Universitat¨ Berlin. In 2010, he established an independent research group within the framework of the Sofja Kovalevskaja program at the Technische Universitat¨ Berlin. Since 2015, he has been on the faculty at the Technische Universita¨ Munchen,¨ where he holds a professorship of silicon chemistry. His current research interests focus on the synthesis, characterization, and reactivity investigation of compounds containing low-valent main group elements (Group 13, 14, and 15 elements) with unusual structures and unique electronic properties, with the goal of finding novel applications in the synthesis and catalysis. vii inorganics Editorial Coordination Chemistry of Silicon Shigeyoshi Inoue WACKER-Institute of Silicon Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748 Garching, Germany; [email protected]; Tel.: +49-89-289-13596 Received: 3 January 2019; Accepted: 7 January 2019; Published: 14 January 2019 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