doi:10.1002/chem.202005289engArauzo, A.Cabeza, J.A.Fernández, I.García-Álvarez, P.García-Rubio, I.Laglera-Gándara, C.J.Reactions of Late First-Row Transition Metal (Fe-Zn) Dichlorides with a PGeP Pincer GermyleneART-2021-124095The reactivity of the PGeP germylene 2, 2’-bis(di-isopropylphosphanylmethyl)-5, 5’-dimethyldipyrromethane-1, 1’-diylgermanium(II), Ge(pyrmPiPr2)2CMe2, with late first-row transition metal (Fe-Zn) dichlorides has been investigated. All reactions led to PGeP pincer chloridogermyl complexes. The reactions with FeCl2 and CoCl2 afforded paramagnetic square planar complexes of formula [MCl{¿3P, Ge, P-GeCl(pyrmPiPr2)2CMe2}] (M=Fe, Co). While the iron complex maintained an intermediate spin state (S1; µeff=3.0 µB) over the temperature range 50–380 K, the effective magnetic moment of the cobalt complex varied linearly with temperature from 1.9 µB at 10 K to 3.6 µB at 380 K, indicating a spin crossover behavior that involves S1/2 (predominant at T<180 K) and S3/2 (predominant at T>200 K) species. Both cobalt(II) species were detected by electron paramagnetic resonance at T<20 K. The reaction of Ge(pyrmPiPr2)2CMe2 with [NiCl2(dme)] (dme=dimethoxyethane) gave a square planar nickel(II) complex, [NiCl{¿3P, Ge, P-GeCl(pyrmPiPr2)2CMe2}], whereas the reaction with CuCl2 involved a redox process that rendered a mixture of the germanium(IV) compound GeCl2(pyrmPiPr2)2CMe2 and a binuclear copper(I) complex, [Cu2{µ-¿3P, Ge, P-GeCl(pyrmPiPr2)2CMe2}2], whose metal atoms are in tetrahedral environments. The reaction of the germylene with ZnCl2 led to the tetrahedral derivative [ZnCl{¿3P, Ge, P-GeCl(pyrmPiPr2)2CMe2}].2021http://zaguan.unizar.es/record/11801410.1002/chem.202005289http://zaguan.unizar.es/record/118014oai:zaguan.unizar.es:118014info:eu-repo/grantAgreement/ES/AEI/PID2019-104652GB-I00info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/RED2018-102387-Tinfo:eu-repo/grantAgreement/ES/MINECO/CTQ2016-75218-Pinfo:eu-repo/grantAgreement/ES/MINECO/CTQ2016-78205-PChemistry - A European Journal 27, 15 (2021), 4985-4992All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/openAccess