Reactions of Late First-Row Transition Metal (Fe-Zn) Dichlorides with a PGeP Pincer Germylene

Arauzo, A. (Universidad de Zaragoza) ; Cabeza, J.A. ; Fernández, I. ; García-Álvarez, P. ; García-Rubio, I. (Universidad de Zaragoza) ; Laglera-Gándara, C.J.

Resumen: The 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}].

Idioma: Inglés

DOI: 10.1002/chem.202005289

Año: 2021

Publicado en: Chemistry - A European Journal 27, 15 (2021), 4985-4992
ISSN: 0947-6539

Factor impacto JCR: 5.02 (2021)

Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 64 / 180 = 0.356 (2021) - Q2 - T2

Factor impacto CITESCORE: 9.1 - Chemical Engineering (Q1)

Factor impacto SCIMAGO: 1.343 - Chemistry (miscellaneous) (Q1) - Catalysis (Q1)

Financiación: info:eu-repo/grantAgreement/ES/AEI/PID2019-104652GB-I00
Financiación: info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/RED2018-102387-T
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2016-75218-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2016-78205-P

Tipo y forma: Artículo (PrePrint)

Área (Departamento): Servicios. Div.Caract.Físi.Quí (Serv.Gral. Apoyo Investigación)
Área (Departamento): Área Física Materia Condensada (Dpto. Física Materia Condensa.)