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All reactions led to PGeP pincer chloridogermyl complexes. The reactions with FeCl<jats:sub>2<\/jats:sub> and CoCl<jats:sub>2<\/jats:sub> afforded paramagnetic square planar complexes of formula [MCl{\u03ba<jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>Ge<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010GeCl(pyrmP<jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>CMe<jats:sub>2<\/jats:sub>}] (M=Fe, Co). While the iron complex maintained an intermediate spin state (<jats:italic>S<\/jats:italic><jats:sup>1<\/jats:sup>; <jats:italic>\u03bc<\/jats:italic><jats:sub>eff<\/jats:sub>=3.0\u2005\u03bc<jats:sub>B<\/jats:sub>) over the temperature range 50\u2013380\u2005K, the effective magnetic moment of the cobalt complex varied linearly with temperature from 1.9\u2005\u03bc<jats:sub>B<\/jats:sub> at 10\u2005K to 3.6\u2005\u03bc<jats:sub>B<\/jats:sub> at 380\u2005K, indicating a spin crossover behavior that involves <jats:italic>S<\/jats:italic><jats:sup>1\/2<\/jats:sup> (predominant at <jats:italic>T<\/jats:italic>&lt;180\u2005K) and <jats:italic>S<\/jats:italic><jats:sup>3\/2<\/jats:sup> (predominant at <jats:italic>T<\/jats:italic>&gt;200\u2005K) species. Both cobalt(II) species were detected by electron paramagnetic resonance at <jats:italic>T<\/jats:italic>&lt;20\u2005K. The reaction of Ge(pyrmP<jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>CMe<jats:sub>2<\/jats:sub> with [NiCl<jats:sub>2<\/jats:sub>(dme)] (dme=dimethoxyethane) gave a square planar nickel(II) complex, [NiCl{\u03ba<jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>Ge<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010GeCl(pyrmP<jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>CMe<jats:sub>2<\/jats:sub>}], whereas the reaction with CuCl<jats:sub>2<\/jats:sub> involved a redox process that rendered a mixture of the germanium(IV) compound GeCl<jats:sub>2<\/jats:sub>(pyrmP<jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>CMe<jats:sub>2<\/jats:sub> and a binuclear copper(I) complex, [Cu<jats:sub>2<\/jats:sub>{\u03bc\u2010\u03ba<jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>Ge<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010GeCl(pyrmP<jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>CMe<jats:sub>2<\/jats:sub>}<jats:sub>2<\/jats:sub>], whose metal atoms are in tetrahedral environments. The reaction of the germylene with ZnCl<jats:sub>2<\/jats:sub> led to the tetrahedral derivative [ZnCl{\u03ba<jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>Ge<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010GeCl(pyrmP<jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>CMe<jats:sub>2<\/jats:sub>}].<\/jats:p>","DOI":"10.1002\/chem.202005289","type":"journal-article","created":{"date-parts":[[2021,1,21]],"date-time":"2021-01-21T14:04:37Z","timestamp":1611237877000},"page":"4985-4992","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":22,"title":["Reactions of Late First\u2010Row Transition Metal (Fe\u2010Zn) Dichlorides with a PGeP Pincer Germylene"],"prefix":"10.1002","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5999-341X","authenticated-orcid":false,"given":"Ana","family":"Arauzo","sequence":"first","affiliation":[{"name":"Instituto de Nanociencia y Materiales de 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