화학공학소재연구정보센터
Inorganic Chemistry, Vol.55, No.4, 1390-1402, 2016
Coordination Complexes of Transition Metals (M = Mo, Fe, Rh, and Ru) with Tin(II) Phthalocyanine in Neutral, Monoanionic, and Dianionic States
The ability of tin atoms to form stable Sn-M bonds with transition metals was used to prepare transition metal complexes with tin(II) phthalocyanine in neutral, monoanionic, and dianionic states. These complexes were obtained via the interactions of [(SnCl2Pc)-Cl-IV(3-)](center dot-) or [(SnPc)-Pc-II(3-)](center dot-) radical anions with {Cp*Mo(CO)(2)}(2), {CpFe(CO)(2)}(2), {CpMo(CO)(3)}(2), Fe-3(CO)(12), {Cp*RhCl2}(2), or Ph5CpRu(CO)(2)Cl. The neutral coordination complexes of Cp*MoBr(CO)(2)[(SnPc)-Pc-II(2-)]center dot 0.5C(6)H(4)Cl(2) (1) and CpFe(CO)(2)[(SnPc)-Pc-II(2-)]center dot 2C(6)H(4)Cl(2) (2) were obtained from [(SnCl2Pc)-Cl-IV(3-)](center dot-). On the other hand, the coordination of transition metals to [(SnPc)-Pc-II(3-)](center dot-) yielded anionic coordination complexes preserving the spin on [(SnPc)-Pc-II(3-)](center dot-). However, in the case of fcryptand[2,2,2](Na+)}{CpFeII(CO)(2)[(SnPc)-Pc-II(4-)]}(-)center dot C6H4Cl2 (4), charge transfer from CpFeI(CO)(2) to [(SnPc)-Pc-II(3-)](center dot-) took place to form the diamagnetic [(SnPc)-Pc-II(4-)](2-) dianion and {CpFeII(CO)(2)}(+). The complexes (cryptand[2,2,2](Na+)}{Fe(CO)(4)[(SnPc)-Pc-II(3-)](center dot-)} (5), fcryptand[2,2,2](Na+)}{CpMo(CO)(2)[(SnPc)-Pc-II(2-)(SnPc)-Pc-II(3-)(center dot-)]} (6), and-(cryptand[2,2,2](Na+)}{Cp*RhCl2[(SnPc)-Pc-II(3-)](center dot-)} (7) have magnetic moments of 1.75, 2.41, and 1.75 mu(B), respectively, owing to the presence of S = 1/2 spins on [(SnPc)-Pc-II(3-)](center dot-) and CpMoI(CO)(2) (for 6). In addition, the strong antiferromagnetic coupling of spins with Weiss temperatures of-35.5-28.6 K was realized between the CpMoI(CO)(2) and the [(SnPc)-Pc-II(3-)](center dot-) units in 6 and the 20-stacking {Fe(CO)(4)[(SnPc)-Pc-II(3-)](center dot-)}(2) dimers of 5, respectively. The [SnuPc(3-)]*- radical anions substituted the chloride anions in Ph3CpRu(CO)(2)Cl to form the formally neutral compound {Ph5CpRuII(CO)(2)[(SnPc)-Pc-II(3-)]} (8) in which the negative charge and spin are preserved on [(SnPc)-Pc-II(3-)](center dot-). The strong antiferromagnetic coupling of spins with a magnetic exchange interaction J/k(B) =-183 K in 8 is explained by the close packing of [(SnPc)-Pc-II(3-)](center dot-) in the pi-stacked-(Ph5CpRuII(CO)(2)[(SnPc)-Pc-II(3-)](center dot-)}(2) dimers.