{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,22]],"date-time":"2026-01-22T02:52:07Z","timestamp":1769050327844,"version":"3.49.0"},"reference-count":51,"publisher":"Wiley","issue":"16","license":[{"start":{"date-parts":[[2018,2,16]],"date-time":"2018-02-16T00:00:00Z","timestamp":1518739200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"name":"Wacker Chemie AG","award":["Silicon Institute"],"award-info":[{"award-number":["Silicon Institute"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2018,3,15]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The reaction of [(Ge<jats:sub>9<\/jats:sub>{Si(TMS)<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>P<jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>)]<jats:sup>\u2212<\/jats:sup> with NHC<jats:sup>Mes<\/jats:sup>CuCl yields [(Ge<jats:sub>9<\/jats:sub>{Si(TMS)<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>)(<jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>P)]Cu(NHC<jats:sup>Mes<\/jats:sup>) (<jats:bold>1<\/jats:bold>), which is a new derivative of the recently reported monomeric zwitterionic tetrel cluster compounds [(Ge<jats:sub>9<\/jats:sub>{Si(TMS)<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>)(<jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>P)]<jats:italic>M<\/jats:italic>(NHC<jats:sup>Dipp<\/jats:sup>) (<jats:italic>M<\/jats:italic>: Cu, Ag, Au). By contrast, the reaction of the same anion [(Ge<jats:sub>9<\/jats:sub>{Si(TMS)<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>P<jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>)]<jats:sup>\u2212<\/jats:sup> with the more labile copper phosphine complex Cy<jats:sub>3<\/jats:sub>PCuCl leads to the formation of [Ge<jats:sub>9<\/jats:sub>{Si(TMS)<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>{(<jats:italic>t<\/jats:italic>Bu)<jats:sub>2<\/jats:sub>PCu}<jats:sub>2<\/jats:sub>Ge<jats:sub>9<\/jats:sub>{Si(TMS)<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>] (<jats:bold>2<\/jats:bold>), which is a neutral dimeric twofold\u2010bridged [Ge<jats:sub>9<\/jats:sub>] cluster compound, with the <jats:italic>exo<\/jats:italic>\u2010bonded phosphine substituent being involved in the cluster bridging. In case of the presence of sterically more demanding phosphines in [Ge<jats:sub>9<\/jats:sub>{Si(TMS)<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>PR<jats:sub>2<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> [R: Mes (<jats:bold>3<\/jats:bold>) and N<jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub> (<jats:bold>4<\/jats:bold>)], reactions with NHC<jats:sup>Dipp<\/jats:sup>CuCl yielded the complexes NHC<jats:sup>Dipp<\/jats:sup>Cu[\u03b7<jats:sup>3<\/jats:sup>\u2010Ge<jats:sub>9<\/jats:sub>{Si(TMS)<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>(PR<jats:sub>2<\/jats:sub>)] [R: Mes (<jats:bold>5<\/jats:bold>) and N<jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub> (<jats:bold>6<\/jats:bold>)], comprising exclusively Cu\u2212Ge bonds. Compounds <jats:bold>5<\/jats:bold> and <jats:bold>6<\/jats:bold> show varying reactivity in dependence of the identity of the phosphine group and represent the first examples of fourfold\u2010substituted [Ge<jats:sub>9<\/jats:sub>] clusters with three different ligands bound to the [Ge<jats:sub>9<\/jats:sub>] cluster core. All compounds were characterized by <jats:sup>1<\/jats:sup>H, <jats:sup>13<\/jats:sup>C, <jats:sup>31<\/jats:sup>P, and <jats:sup>29<\/jats:sup>Si NMR spectroscopy. Additionally, compounds <jats:bold>3<\/jats:bold> and <jats:bold>4<\/jats:bold> were analyzed by ESI\u2010MS, and the structures of compounds <jats:bold>1<\/jats:bold>, <jats:bold>2<\/jats:bold>, and <jats:bold>5<\/jats:bold> were characterized by single\u2010crystal X\u2010ray diffraction.<\/jats:p>","DOI":"10.1002\/chem.201705678","type":"journal-article","created":{"date-parts":[[2018,1,11]],"date-time":"2018-01-11T04:24:53Z","timestamp":1515644693000},"page":"4103-4110","source":"Crossref","is-referenced-by-count":28,"title":["On the Variable Reactivity of Phosphine\u2010Functionalized [Ge<sub>9<\/sub>] Clusters: <i>Zintl<\/i> Cluster\u2010Substituted Phosphines or Phosphine\u2010Substituted <i>Zintl<\/i> Clusters"],"prefix":"10.1002","volume":"24","author":[{"given":"Felix S.","family":"Geitner","sequence":"first","affiliation":[{"name":"WACKER Institute for Silicon Chemistry and Department Chemie Technische Universit\u00e4t M\u00fcnchen  Lichtenbergstra\u00dfe 4 85747 Garching b. M\u00fcnchen Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Christoph","family":"Wallach","sequence":"additional","affiliation":[{"name":"Department Chemie Technische Universit\u00e4t M\u00fcnchen  Lichtenbergstra\u00dfe 4 85747 Garching b. M\u00fcnchen Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9460-8882","authenticated-orcid":false,"given":"Thomas F.","family":"F\u00e4ssler","sequence":"additional","affiliation":[{"name":"Department Chemie Technische Universit\u00e4t M\u00fcnchen  Lichtenbergstra\u00dfe 4 85747 Garching b. M\u00fcnchen Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2018,2,16]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00069a003"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200460427"},{"key":"e_1_2_7_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200460427"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/om060480o"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201001630"},{"key":"e_1_2_7_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201001630"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00234a026"},{"key":"e_1_2_7_7_1","unstructured":"\u00a0"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic702151q"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201100412"},{"key":"e_1_2_7_10_1","unstructured":"\u00a0"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic202744d"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200250683"},{"key":"e_1_2_7_12_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200250683"},{"key":"e_1_2_7_13_1","unstructured":"\u00a0"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201600258"},{"key":"e_1_2_7_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201603475"},{"key":"e_1_2_7_16_2","doi-asserted-by":"publisher","DOI":"10.1039\/b901870k"},{"key":"e_1_2_7_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.201600295"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1039\/c1dt10096c"},{"key":"e_1_2_7_19_1","unstructured":"\u00a0"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200700530"},{"key":"e_1_2_7_20_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200700530"},{"key":"e_1_2_7_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/b717506j"},{"key":"e_1_2_7_22_2","doi-asserted-by":"publisher","DOI":"10.1039\/b906551b"},{"key":"e_1_2_7_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201603441"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201601134"},{"key":"e_1_2_7_25_1","unstructured":"\u00a0"},{"key":"e_1_2_7_26_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5DT04022A"},{"key":"e_1_2_7_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.7b01186"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.3390\/molecules22071204"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b06545"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b08562"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b05834"},{"key":"e_1_2_7_32_1","unstructured":"\u00a0"},{"key":"e_1_2_7_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/om201198s"},{"key":"e_1_2_7_34_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20000717)39:14<2478::AID-ANIE2478>3.0.CO;2-G"},{"key":"e_1_2_7_34_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20000717)112:14<2596::AID-ANGE2596>3.0.CO;2-C"},{"key":"e_1_2_7_35_2","doi-asserted-by":"publisher","DOI":"10.1039\/b510253g"},{"key":"e_1_2_7_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja017011s"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200901038"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201603374"},{"key":"e_1_2_7_38_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201603374"},{"key":"e_1_2_7_39_1","unstructured":"\u00a0"},{"key":"e_1_2_7_40_2","doi-asserted-by":"publisher","DOI":"10.1186\/1860-5397-3-22"},{"key":"e_1_2_7_41_2","doi-asserted-by":"publisher","DOI":"10.1039\/c3cc45488f"},{"key":"e_1_2_7_42_2","doi-asserted-by":"publisher","DOI":"10.1039\/b111121n"},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1107\/S2053229614024218"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1107\/S090744490804362X"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/om100106e"}],"container-title":["Chemistry 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