{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,8]],"date-time":"2026-01-08T22:11:22Z","timestamp":1767910282649,"version":"3.49.0"},"reference-count":54,"publisher":"MDPI AG","issue":"14","license":[{"start":{"date-parts":[[2023,7,16]],"date-time":"2023-07-16T00:00:00Z","timestamp":1689465600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"German Federal Ministry of Environment, Nature Conservation, Nuclear Safety, and Consumer Protection (BMUV)","award":["1501667"],"award-info":[{"award-number":["1501667"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Phenylgermaniumpyridine-2-olate PhGe(pyO)3 (compound 1Ge) and CuCl react with the formation of the heteronuclear complex Ph(pyO)Ge(\u03bc2-pyO)2CuCl (2Ge\u2019) rather than forming the expected compound PhGe(\u03bc2-pyO)3CuCl (2Ge). Single-point calculations (at the B2T-PLYP level) of the optimized molecular structures confirmed the relative stability of isomer 2Ge\u2019 over 2Ge and, for the related silicon congeners, the relative stability of 2Si over 2Si\u2019. Decomposition of a solution of 2Ge\u2019 upon access to air provided access to some crystals of the copper(II) compound PhGe(\u03bc2-pyO)4CuCl (3Ge). Compounds 2Ge\u2019 and 3Ge were characterized by single-crystal X-ray diffraction analyses, and the Ge\u2013Cu 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(\u03bc2-pyO)3CuCl (2Si), PhSi(\u03bc2-pyO)4CuCl (3Si), as well as the potential isomers Ph(pyO)Si(\u03bc2-pyO)2CuCl (2Si\u2019) and PhGe(\u03bc2-pyO)3CuCl (2Ge). Pronounced Cu\u2192Ge (over Cu\u2192Si) lone pair donation was found for the Cu(I) compounds, whereas in Cu(II) compounds 3Si and 3Ge, this \u03c3-donation is less pronounced and only marginally enhanced in 3Ge over 3Si.<\/jats:p>","DOI":"10.3390\/molecules28145442","type":"journal-article","created":{"date-parts":[[2023,7,17]],"date-time":"2023-07-17T00:56:47Z","timestamp":1689555407000},"page":"5442","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Ge\u2013Cu-Complexes Ph(pyO)Ge(\u03bc2-pyO)2CuCl and PhGe(\u03bc2-pyO)4CuCl\u2014Representatives of Cu(I)\u2192Ge(IV) and Cu(II)\u2192Ge(IV) Dative Bond Systems"],"prefix":"10.3390","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5968-2331","authenticated-orcid":false,"given":"J\u00f6rg","family":"Wagler","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie, TU Bergakademie Freiberg, 09596 Freiberg, Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4669-0206","authenticated-orcid":false,"given":"Robert","family":"Gericke","sequence":"additional","affiliation":[{"name":"Institute of Resource Ecology, Helmholtz-Zentrum Dresden-Rossendorf eV, 01328 Dresden, Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2023,7,16]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"59","DOI":"10.1016\/j.jorganchem.2012.01.019","article-title":"Transition metal compounds containing alkynylsilyl groups\u2014Complexes with a metal-silicon bond","volume":"705","author":"Hoffmann","year":"2012","journal-title":"J. Organomet. Chem."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"8059","DOI":"10.1021\/om300915y","article-title":"Anionic Iron Complexes with a Bond between an Ate-Type Pentacoordinated Germanium and an Iron Atom","volume":"31","author":"Kano","year":"2012","journal-title":"Organometallics"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"127","DOI":"10.1016\/0022-328X(95)00508-N","article-title":"A new approach to the formal classification of covalent compounds of the elements","volume":"500","author":"Green","year":"1995","journal-title":"J. Organomet. Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"2759","DOI":"10.1002\/(SICI)1521-3773(19990917)38:18<2759::AID-ANIE2759>3.0.CO;2-P","article-title":"The sting of the Scorpion: A Metallaboratrane","volume":"38","author":"Hill","year":"1999","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"2588","DOI":"10.1021\/ic051975t","article-title":"Synthesis and Structural Characterization of [\u03ba3-B,S,S-B(mimR)3]Ir(CO)(PPh3)H (R = But, Ph) and [[\u03ba4-B(mimBut)3]M(PPh3)Cl (M = Rh, Ir): Analysis of the Bonding in Metal Borane Compounds","volume":"45","author":"Landry","year":"2006","journal-title":"Inorg. Chem."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"5396","DOI":"10.1021\/jacs.0c00905","article-title":"Rare-Earth Supported Nickel Catalysts for Alkyne Semihydrogenation: Chemo- and Regioselectivity Impacted by the Lewis Acidity and Size of the Support","volume":"142","author":"Ramirez","year":"2020","journal-title":"J. Am. Chem. Soc."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"16833","DOI":"10.1002\/chem.202003167","article-title":"Metal-only Lewis Pairs of Rhodium with s, p and d-Block Metals","volume":"26","author":"Bajo","year":"2020","journal-title":"Chem. Eur. J."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"624","DOI":"10.1002\/anie.200905241","article-title":"Metallasilatranes: Palladium(II) and Platinum(II) as Lone-Pair Donors to Silicon(IV)","volume":"49","author":"Wagler","year":"2010","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"15541","DOI":"10.1021\/acs.inorgchem.0c02615","article-title":"Trivalent Antimony as L-, X-, and Z-Type Ligand: The Full Set of Possible Coordination Modes in Pt\u2212Sb Bonds","volume":"59","author":"Gericke","year":"2020","journal-title":"Inorg. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1837","DOI":"10.1021\/acs.inorgchem.5b02740","article-title":"The Effect of Substituents at Lewis Acidic Bismuth(III) Centers on Its Propensity to Bind a Noble Metal Donor","volume":"55","author":"Tschersich","year":"2016","journal-title":"Inorg. Chem."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"3864","DOI":"10.1002\/anie.201300337","article-title":"Telluronium Ions as \u03c3-Acceptor Ligands","volume":"52","author":"Lin","year":"2013","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"4239","DOI":"10.1002\/anie.200900521","article-title":"Complexes with Dative Bonds between d- and s-Block Metals: Synthesis and Structure of [(Cy3P)2Pt \u2212 Be(Cl)X] (X = Cl, Me)","volume":"48","author":"Braunschweig","year":"2009","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Ehrlich, L., Gericke, R., Brendler, E., and Wagler, J. (2018). (2-Pyridyloxy)silanes as Ligands in Transition Metal Coordination Chemistry. Inorganics, 6.","DOI":"10.3390\/inorganics6040119"},{"key":"ref_14","doi-asserted-by":"crossref","unstructured":"Seidel, A., Gericke, R., Brendler, E., and Wagler, J. (2023). Copper Complexes of Silicon Pyridine-2-olates RSi(pyO)3 (R = Me, Ph, Bn, Allyl) and Ph2Si(pyO)2. Inorganics, 11.","DOI":"10.3390\/inorganics11010002"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"583","DOI":"10.1002\/zaac.19956210416","article-title":"Alternativ-Liganden. XXXII Neue Tetraphosphan-Nickelkomplexe mit Tripod-Liganden des Typs XM\u2019(OCH2PMe2)n(CH2CH2PR2)3-n (M\u2019 = Si, Ge; n = 0\u20133)","volume":"621","author":"Grobe","year":"1995","journal-title":"Z. Anorg. Allg. Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"5004","DOI":"10.1039\/D1CC01392K","article-title":"Pd\/Ni-Catalyzed Germa-Suzuki coupling via dual Ge\u2013F bond activation","volume":"57","author":"Kameo","year":"2021","journal-title":"Chem. Commun."},{"key":"ref_17","unstructured":"(2023, June 09). ConQuest. Version 2023.1.0. Available online: https:\/\/www.ccdc.cam.ac.uk\/solutions\/software\/conquest\/."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1440","DOI":"10.1021\/om501159v","article-title":"Evaluation of the \u03c3-Donation from Group 11 Metals (Cu, Ag, Au) to Silane, Germane, and Stannane Based on the Experimental\/Theoretical Systematic Approach","volume":"34","author":"Kameo","year":"2015","journal-title":"Organometallics"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"4909","DOI":"10.1021\/om9006196","article-title":"Spectroscopic and Structural Characterization of Copper-Germylene Complexes Bearing an Isopropyl-Substituted \u03b2-Diketiminate Ligand","volume":"28","author":"Arii","year":"2009","journal-title":"Organometallics"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"4985","DOI":"10.1002\/chem.202005289","article-title":"Reactions of Late First-Row Transition Metal (Fe-Zn) Dichloride with a PGeP Pincer Germylene","volume":"27","author":"Arauzo","year":"2021","journal-title":"Chem. Eur. J."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"3301","DOI":"10.1002\/ejic.202100523","article-title":"N\u2192Ge Coordinated Germylenes as Ligands for Monomeric Cu Complexes","volume":"2021","author":"Mikysek","year":"2021","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_22","doi-asserted-by":"crossref","unstructured":"Ku\u00df, S., Brendler, E., and Wagler, J. (2022). Molecular Structures of the Pyridine-2-olates PhE(pyO)3 (E = Si, Ge, Sn) \u2212 [4+3]-Coordination at Si, Ge vs. Heptacoordination at Sn. Crystals, 12.","DOI":"10.3390\/cryst12121802"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"4813","DOI":"10.1021\/acs.inorgchem.6b00210","article-title":"[(NHC)CuI\u2212ER3 ] Complexes (ER3 = SiMe2Ph, SiPh3, SnMe3 ): From Linear, Mononuclear Complexes to Polynuclear Complexes with Ultrashort CuI\u22efCuI Distances","volume":"55","author":"Plotzitzka","year":"2016","journal-title":"Inorg. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"5083","DOI":"10.1021\/ic025715c","article-title":"Synthesis and Reactions of Triphenylsilanethiolato Complexes of Manganese(II), Iron(II), Cobalt(II), and Nickel(II)","volume":"41","author":"Komuro","year":"2002","journal-title":"Inorg. Chem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"955","DOI":"10.1039\/B617136B","article-title":"Structural variation in copper(I) complexes with pyridylmethylamide ligands: Structural analysis with a new four-coordinate geometry index, \u03c44","volume":"36","author":"Yang","year":"2007","journal-title":"Dalton Trans."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"6357","DOI":"10.1002\/anie.201002995","article-title":"A Mercury\u2192Antimony Interaction","volume":"49","author":"Lin","year":"2010","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"7145","DOI":"10.1021\/ic400736b","article-title":"\u03c3-Donor\/Acceptor-Confused Ligands: The Case of a Chlorostibine","volume":"52","author":"Ke","year":"2013","journal-title":"Inorg. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"14039","DOI":"10.1021\/jacs.0c04690","article-title":"Fluorosilane Activation by Pd\/Ni\u2192Si\u2212F\u2192Lewis Acid Interaction: An Entry to Catalytic Sila-Negishi Coupling","volume":"142","author":"Kameo","year":"2020","journal-title":"J. Am. Chem. Soc."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"9892","DOI":"10.1002\/anie.200905391","article-title":"Gold\u2013Silane and Gold\u2013Stannane Complexes: Saturated Molecules as \u03c3-Acceptor Ligands","volume":"48","author":"Gualco","year":"2009","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"18122","DOI":"10.1021\/acs.inorgchem.1c02735","article-title":"Coordination and Electrochemical Switching on Paddle-Wheel Complexes Containing an As\u2212Ru or a Sb\u2212Ru Axis","volume":"60","author":"Gericke","year":"2021","journal-title":"Inorg. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"2832","DOI":"10.1039\/b801115j","article-title":"Covalent radii revisited","volume":"37","author":"Cordero","year":"2008","journal-title":"Dalton Trans."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"1329","DOI":"10.1002\/anie.201810056","article-title":"Intercepting the Disilene-Silylsilylene Equilibrium","volume":"58","author":"Stanford","year":"2019","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"4744","DOI":"10.1039\/C4DT03903C","article-title":"Tp*Cu(I)\u2013CN\u2013SiL2\u2013NC\u2013Cu(I)Tp*\u2014A hexacoordinate Si-complex as connector for redox active metals via \u03c0-conjugated ligands","volume":"44","author":"Brendler","year":"2015","journal-title":"Dalton Trans."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1107\/S2053273314026370","article-title":"SHELXT\u2014Integrated space-group and crystal-structure determination","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Acta Crystallogr. A"},{"key":"ref_35","unstructured":"Sheldrick, G.M. (2018). Program for the Refinement of Crystal Structures, University of G\u00f6ttingen. SHELXL-2018\/3."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1107\/S2053229614024218","article-title":"Crystal structure refinement with SHELXL","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Acta Crystallogr. C"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"565","DOI":"10.1107\/S0021889897003117","article-title":"ORTEP-3 for windows\u2014A version of ORTEP-III with a graphical user interface (GUI)","volume":"30","author":"Farrugia","year":"1997","journal-title":"J. Appl. Crystallogr."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"849","DOI":"10.1107\/S0021889812029111","article-title":"WinGX and ORTEP for Windows: An update","volume":"45","author":"Farrugia","year":"2012","journal-title":"J. Appl. Crystallogr."},{"key":"ref_39","unstructured":"(2021, June 28). POV-RAY (Version 3.7), Trademark of Persistence of Vision Raytracer Pty. Ltd., Williamstown, Victoria (Australia). Copyright Hallam Oaks Pty. Ltd., 1994\u20132004. Available online: http:\/\/www.povray.org\/download\/."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"e1606","DOI":"10.1002\/wcms.1606","article-title":"Software update: The ORCA program system\u2014Version 5.0","volume":"8","author":"Neese","year":"2022","journal-title":"WIREs Comput. Mol. Sci."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"3297","DOI":"10.1039\/b508541a","article-title":"Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy","volume":"7","author":"Weigend","year":"2005","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"363","DOI":"10.1002\/wcms.1177","article-title":"All-electron basis sets for heavy elements","volume":"4","author":"Pantazis","year":"2014","journal-title":"WIREs Comput. Mol. Sci."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"4597","DOI":"10.1063\/1.466059","article-title":"Relativistic regular two-component Hamiltonians","volume":"99","author":"Baerends","year":"1993","journal-title":"J. Chem. Phys."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"392","DOI":"10.1063\/1.476576","article-title":"Molecular density functional calculations in the regular relativistic approximation: Method, application to coinage metal diatomics, hydrides, fluorides and chlorides, and comparison with first-order relativistic calculations","volume":"109","year":"1998","journal-title":"J. Chem. Phys."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"1456","DOI":"10.1002\/jcc.21759","article-title":"Effect of the damping function in dispersion corrected density functional theory","volume":"32","author":"Grimme","year":"2011","journal-title":"J. Comput. Chem."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"154104","DOI":"10.1063\/1.3382344","article-title":"A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu","volume":"132","author":"Grimme","year":"2010","journal-title":"J. Chem. Phys."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"554","DOI":"10.1021\/acs.jctc.6b01041","article-title":"Automatic Generation of Auxiliary Basis Sets","volume":"13","author":"Stoychev","year":"2017","journal-title":"J. Chem. Theory Comput."},{"key":"ref_48","unstructured":"Glendening, E.D., Badenhoop, J.K., Reed, A.E., Carpenter, J.E., Bohmann, J.A., Morales, C.M., Karafiloglou, P., Landis, C.R., and Weinhold, F. (2022, February 03). NBO, Available online: http:\/\/nbo7.chem.wisc.edu\/."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"580","DOI":"10.1002\/jcc.22885","article-title":"Multiwfn: A Multifunctional Wavefunction Analyzer","volume":"33","author":"Lu","year":"2012","journal-title":"J. Comput. Chem."},{"key":"ref_50","unstructured":"(2015, September 19). Chemcraft, Version 1.8 (Build 164). Available online: http:\/\/www.chemcraftprog.com\/."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"33","DOI":"10.1016\/0263-7855(96)00018-5","article-title":"VMD: Visual molecular dynamics","volume":"14","author":"Humphrey","year":"1996","journal-title":"J. Molec. Graphics"},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"268","DOI":"10.1002\/tcr.201600061","article-title":"Saturated Heavier Group 14 Compounds as \u03c3-Electron-Acceptor (Z-Type) Ligands","volume":"17","author":"Kameo","year":"2017","journal-title":"Chem. Rec."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"5702","DOI":"10.1039\/D1CP00242B","article-title":"Origins and properties of the tetrel bond","volume":"23","author":"Scheiner","year":"2021","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_54","unstructured":"Scheiner, S. (2019). Special Issue \u201cTetrel Bonds\u201d, MDPI. Available online: https:\/\/www.mdpi.com\/journal\/molecules\/special_issues\/Tetrel_Bonds."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/28\/14\/5442\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T20:12:59Z","timestamp":1760127179000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/28\/14\/5442"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,7,16]]},"references-count":54,"journal-issue":{"issue":"14","published-online":{"date-parts":[[2023,7]]}},"alternative-id":["molecules28145442"],"URL":"https:\/\/doi.org\/10.3390\/molecules28145442","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,7,16]]}}}