174865-79-3Relevant academic research and scientific papers
Synthesis and characterization of cyclometallated complexes of palladium(II) and manganese(I) with bidentate Schiff bases
Vila, Jose M.,Gayoso, Miguel,Pereira, M. Teresa,Loepez Torres, Margarita,Fernandez, Jesus J.,Fernandez, Alberto,Ortigueira, Juan M.
, p. 165 - 174 (2007/10/02)
Treatment of N,N-isophthalylidenebis(cyclohexylamine), 1,3-(CyN = CH)2C6H4 (L2) (Cy = cyclohexyl) with palladium(II) acetate in glacial acetic acid gave after column chromatography the monocyclometallated dimer complex [{Pd[3-(CHO)C6H3C(H)=NCy](O2CMe)}2] (1) with a free formyl group on each phenyl ring, and a mixture of 1 with the doubly cyclometallated complex [Pd{3-(CyN=CH)C6H3C(H)=NCy}(O2CMe)] (2). Treatment of 1 with cyclohexylamine gave the correspond ing dimer complex [{Pd[3-(CyN=CH)C6H3C(H)=NCy](O2CMe)}2] (17) with an uncoordinated C=N group on each phenyl ring. Treatment of 1 and 2 with aqueous NaX gave the dimer complexes [{Pd[3-(CHO)C6H3C(H)=NCy](X)}2] (3: X = Cl; 4: X = Br; 5: X = I) and a mixture of 3, 4 or 5 with the doubly cyclometallated complex [Pd{3-(CyN=CH)C6H3C(H)=NCy}(X)] (6: X - Cl; 7: X = Br; 8: X = I), respectively. The dicyclometallated iodo complex 8 was isolated pure. Treatment of 3, 4 or 5 with cyclohexylamine in a 1:2 or 1:4 molar ratio gave the cyclometallated complexes [Pd{3-(CHO)C6H3C(H)=NCy}(X)(NH2Cy)] (9: X = Cl; 10: X = Br; 11: X = I) and [Pd{3-(CyN=CH)C6H3C(H)=NCy}(X)(NH2Cy)] (12: X = Cl; 13: X = Br; 14: X = I), respectively; the last three compounds each contain an uncoordinated C=N group. The corresponding bromo and iodo analogues were made similarly. Treatment of 3, 4 or 5 with thallium cyclopentadienyl or thallium acetylacetonate gave the mononuclear complexes [Pd{3-(CHO)C6H3C(H)=NCy}(C5H5)] (15) and [Pd{3-(CHO)C6H3C(H)=NCy}H3CCOCHCOCH3)] (16), respectively. Treatment of L2 with MnMe(CO)5 in a 1:1 molar ratio gave the monocyclometallated complex [(OC)4Mn{3-(CHO)C6H3C(H)=NCy}] (18) by cleavage of one C=N bond, whereas treatment of L2 with MnMe(CO)5 in a 1:1.2 molar ratio produced a mixture of the doubly cyclometallated complex 19 and the monocyclometallated complex 20 without cleavage of the C=N bond. Treatment of N,N-terephthalylidenebis(cyclohexylamine), 1,4-(CyN=CH)2C6H4 (L1) (Cy = cyclohexyl), with MnMe(CO)5 in a 1:1.2 molar ratio gave a mixture of the monocyclometallated compound [(OC)4Mn{4-(CHO)C6H3C(H)=NCy}] (22) and the monocyclometallated compound [(OC)4Mn{4-(CyN=CH)C6H3C(H)=NCy}] (23); compound 22 was isolated in a pure state.
