Chromium(III) complexes with 1,5,9-triazanonane (3,3-tri) - CrX3(3,3-tri)n+ and CrCl(diamine)(3,3-tri)2+

摘要: The reaction of CrCl3 · 6H2O (dehydrated in DMSO) with 1,5,9-triazanonane (3,3-tri) gives mer- CrCl3(3,3-tri), the configuration being established by isomorphism corresponding Co(III) complex. This non-electrolyte is hydrolyzed aqueous acidic solution and mer-[CrCl2(3,3-tri)- (OH2)]ClO4 can be isolated anation HCl presence HClO4. Reaction mer-CrCl3- DMF diamines produces complexes type [CrCl(diamine)(3,3-tri)] Cl2 [diamine= 1,2-diaminoethane (en), 1.2-diaminopropane (pn), 1,3-diaminopropane (tn), 2,2-dimethyl-1,3-diaminopropane (Me2tn) cyclohexanediamine (chxn, cis plus trans mixture; two isomers A B)] these have been characterized as ZnCl42− salts. triamine ligand has mer-(H↓)- a single crystal X-ray analysis [CrCl(en)(3,3-tri)]- ZnCl4, monoclinic, P21, a=7.932, b= 14.711, c= 8.312 A, β=104.6° Z=2, refined to conventional R factor 0.034. kinetics Hg2+- assisted chloride release from [CrCl(diamine)(3,3- tri)]ZnCl4 salts were measured spectrophotometrically (μ=1.0 M HClO4 or HNO3) over 15 K temperature ranges give, order, 104kHg (298.2 K) (M−1 s−1), Ea(kJ mol−1), ΔS# (J K−1 mol−1): en- (HClO4): 5.95, 78.1, -53; pn(HClO4); 5.24, 81.2; -44; tn(HClO4): 26.7, 85.6, -15; Me2tn(HClO4): 21.8, 78.6, -40; A-chxn(HNO3): 7.60, 81.0,-41; B-chxn(HNO3): 18.3, 56.8, -115. ‘non-replaced effect’ on rate observed for first time this series homologous Cr(III) complexes. thermal aquation (kH, 0.1 HClO4) titrimetrically CrCl(diamine) (3,3-tri)2+ give following kinetic parameters: diamine=en: 107kH (298.2)=5.34 s−1, Ea=99.2 kJ mol−1, ΔS#=-40 J mol-1; diamine =tn: (298.2)=5.04 Ea= 82.8, ΔS#= -96.