Übergangsmetallorganisch stabilisierte Indate und Germanate: Synthese, Struktur und Eigenschaften der Komplexe [{(CO)₅M}EX₃]^2– (M = Cr, Mo, W; E = In; X = Cl, Br), [(CO₅Cr)InBr(μ²-Br)]₂ ^2– sowie [{(CO)₅Cr}E(oxinat)₂]^n– (E = In, n = 2; E = Ge, n = 1) / Organometallically Protected Indates and Germanates: Synthesis, Structure and Properties of [{(CO)₅M}EX₃]^2- (M = Cr, Mo, W; E = In; X = Cl, Br), [(CO₅Cr)InBr(μ²-Br)]₂ ^2- and [{(CO)₅Cr}E(oxinat)₂]^n- (E = In, n = 2; E = Ge, n = 1)

Abstract

A novel route to reactive In(I)-complexes [{(CO) 5 M}InXּTHF] (M = Cr, X = Cl, Br; M = Mo, X = Cl; M = Mo, X = Cl) is described. With an excess of tetraphenylphosphonium halides [Ph 4 P]X (X = Cl, Br) these compounds react to give trihaloindate-complexes [Ph 4 P] 2 ּ [{(CO) 5 M}InX 3 ] (M = Cr, X = Cl: 1a, X = Br: 1b; M = Mo, X = Cl: 2; M = W, X = Cl: 3), which contain indium in a formal oxidation state of +I. The reaction of equimolar ammounts of [{(CO) 5 Cr}InBrּTHF] and bromide ions gives the bridged, dinuclear compound [{(CO) 5 Cr}InBr(μ 2 -Br)] 2 2- (4). 4 is an intermediate in the reaction of [{(CO) 5 Cr}InBrּTHF] to [{(CO) 5 Cr}InBr 3 ] 2- , 1b. Reaction of sodium-8-hydoxychinolate and [{(CO) 5 Cr}InClּTHF] produces the anion [{(CO) 5 Cr}In(oxinat) 2 ] - (5) which contains In(+I) in a square pyramidal coordination geometry. [{(CO) 5 Cr}GeI 3 ] - , which is isoelectronic to 1-3, reacts with 8-hydroxyquinoline to produce [{(CO) 5 Cr}Ge(oxinat) 2 ] (6) which is isoelectronic to 5. All new compounds have been characterized by X-ray analysis and by the usual analytic and spectroscopic techniques. 115 In NMR spectra of M(CO) 5 substituted indium species (M = Cr, Mo, W) are reported for the first time.