Synthesis, characterization and crystal structures of cyclometallated palladium (II) compounds containing difunctional ligands with [P,P], [As,As], [N,N], [P,As], [P,N] and [P,O] donor atoms

Autor: José M. Vila, Raquel Ares, Alberto Fernández, Nina Gómez-Blanco, Digna Vázquez-García, Margarita López-Torres, Jesús J. Fernández
Rok vydání: 2008
Předmět:
Zdroj: Journal of Organometallic Chemistry. 693:3655-3667
ISSN: 0022-328X
DOI: 10.1016/j.jorganchem.2008.08.023
Popis: Treatment of the chloro-bridged dinuclear complex [Pd{3,4-(MeO) 2 C 6 H 2 C(H) N(Cy)- C 6, N }(μ-Cl)] 2 ( 1 ) with homobidentate [ P , P ], [ As , As ], [ N , N ], and heterobidentate [ P , As ], [ P , N ] ligands in a 1:1 molar ratio gave the dinuclear complexes [{Pd[3,4-(MeO) 2 C 6 H 2 C(H) N(Cy)- C 6, N ](Cl)} 2 {μ-L}] (L = Ph 2 PC 4 H 6 (NH)CH 2 PPh 2 ( 2 ); Ph 2 As(CH 2 ) 2 AsPh 2 ( 3 ); 1,3-(NH 2 CH 2 ) 2 C 6 H 4 ( 4 ); Ph 2 P(CH 2 ) 2 AsPh 2 ( 5 ); Ph 2 P(CH 2 ) 2 NH 2 ( 6 )), with the bidentate ligands bridging the two cyclometallated fragments. The reaction with the homobidentate ligands in a 1:2 molar ratio in the presence of NaClO 4 afforded the mononuclear compounds [[Pd{3,4-(MeO) 2 C 6 H 2 C(H) N(Cy)- C 6, N }{L- P , P }][ClO 4 ] (L = Ph 2 PC 4 H 6 (NH)CH 2 PPh 2 ( 7 ); ( o -Tol) 2 P(CH 2 ) 2 P( o -Tol) 2 ( 8 )), [Pd{3,4-(MeO) 2 C 6 H 2 C(H) N(Cy)- C 6, N }{Ph 2 As(CH 2 ) 2 AsPh 2 - As , As }][ClO 4 ] ( 9 ) and [Pd{3,4-(MeO) 2 C 6 H 2 C(H) N(Cy)- C 6, N }{L- N , N }][ClO 4 ] (L = NH 2 (CH 2 ) 3 NH 2 ( 10 ); NH 2 (C 6 H 8 )CH 2 (C 6 H 8 )NH 2 ( 11 ); 1,3-(NH 2 CH 2 ) 2 C 6 H 4 ( 12 ); 1,3-(NH 2 ) 2 C 5 H 3 N ( 13 ); NH 2 (C 6 H 4 )O(C 6 H 4 )NH 2 ( 14 ); NMe 2 (CH 2 ) 2 NMe 2 ( 15 )), in which the chloro ligands are absent and the bidentate ligands are chelated to the palladium atom. Reaction of 1 with Ph 2 P(CH 2 ) 2 AsPh 2 in 1:2 molar ratio in acetone in the presence of NH 4 PF 6 afforded the analogous mononuclear compound [Pd{3,4-(MeO) 2 C 6 H 2 C(H) N(Cy)- C 6, N }{Ph 2 P(CH 2 ) 2 AsPh 2 - P , As }][PF 6 ] ( 16 ); whereas reaction with Ph 2 P(CH 2 ) 3 NH 2 gave [Pd{3,4-(MeO) 2 C 6 H 2 C(H) N(Cy)- C 6, N }{Ph 2 P(CH 2 ) 3 N(C Me 2 )- P , N }][PF 6 ] ( 17 ), derived from intermolecular condensation between the aminophosphine and acetone. Condensation of the NH 2 group was precluded by change of solvent, using dichloromethane. Iminophoshines also reacted with 1 in 1:2 molar ratio in acetone to give a new series of mononuclear cyclometallated complexes: [Pd{3,4-(MeO) 2 C 6 H 2 C(H) N(Cy)- C 6, N }{L- P , N }][ClO 4 ] (L = Ph 2 PC 6 H 4 C(H) NCy ( 20 ); Ph 2 PC 6 H 4 C(H) NC(CH 3 ) 3 ( 21 ); Ph 2 PC 6 H 4 C(H) NNMe 2 ( 22 ); Ph 2 PC 6 H 4 C(H) NNHMe ( 23 ); Ph 2 PC 6 H 4 C(H) NNHPh ( 24 )). Analogous complexes with a stable P , O -chelate were obtained using bidentate [ P , O ] donor ligands: [Pd{3,4-(MeO) 2 C 6 H 2 C(H) N(Cy)- C 6, N }{L- P , O }][Cl] (L = 2-(Ph 2 P)C 6 H 4 CHO ( 25 ); Ph 2 PN(Me)C( O)Me ( 26 )). The crystal structures of compounds 1 , 5 , 15 , 16 , 18 , 20 have been determined by X-ray crystallography.
Databáze: OpenAIRE
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