摘要:
Reaction of the cyclometallated compounds [Pd{2,3,4-(MeO)(3)C6HC(H)=N[(2)-(O)-5-RC6H3]}](4) (1a: R = H, 1b: R = 'Bu) with the phosphine PPh2[2-(COH)C6H4], in a complex/phosphine 1:4 molar ratio gave the mononuclear cyclometallated complexes [{Pd{2,3,4(MeO)(3)C6HC(H)=N[2-(O)-5-RC6H3)) {PPh2[2-(HOC)C6H4]}] (2a: R = H; 2b: R =Bu-t), upon cleavage of the tetranuclear structure. Treatment of complex 1a with the diarsine AsPh2(CH2)(2)Ph2As (dppae) in a 1:2 or 1:4 molar ratio only yielded the dinuclear compound [{Pd{2,3,4-(MeO)(3)C6HC(H)=N[2-(O)C6H4]}}(2){mu-AsPh2(CH2)(2)Ph2As] (3a), regardless the molar ratio used. Reaction of the cyclometallated tetramers with Ph2P(CH2)(2)Ph2As (arphos) in a 1:4 molar ratio gave the mononuclear cyclometallated complexes [Pd{2,3,4(MeO)(3)C6HC(H)=N[2-(O)C6H4]}}(2){mu-PPh2(CH2)(2)Ph2As}] (4a) and [Pd{2,3,4-(MeO)(3)C6HC(H)=N[2-(O)-5-BuC6H3]}{PPh2(CH2)(2)PhAs-P}] (4b), with the P,As ligand coordinated through the phosphorus atom, as air-stable solids. Treatment of la with arphos in a 1:2 molar ratio gave the dinuclear complex [{Pd{2,3,4-(MeO)(3)C6HC(H)=N[2-(O)C6H4]}}(2){mu-PPh2(CH2)(2)Ph2As)] (5a). Reaction of 1b with the diphosphine Ph2P(C6H4)O(C6H4)PPh2 gave the dinuclear compound [{Pd{2,3,4-(MeO)(3)C6HC(H)=N[2-(O)-(BuC6H3)-Bu-t]}}2 {mu-PPh2(C6H4)O(C6H4)Ph2P}] (6b) for all the complex 1b/phosphine molar ratios tested. Reaction of the cyclometallated tetramer la with PPh2[4-(NMe2)C6H4] (in 1:2 or 1:4 molar ratio) produced the mononuclear cyclometallated complex [Pd{2,3,4(MeO)(3)C6HC(H)=N[2-(O)C6H4]}{PPh2[4-(NMe2)C6H4]}] (7a) as an air-stable solid. (c) 2007 Elsevier Ltd. All rights reserved.