Synthesis and structural characterization of boron subphthalocyaninates

Halosubphthalocyaninatoboron, [B(X)(s)pc] (X = F, Cl, Br) is obtained by he ating phthalonitrile with baron trihalide in quinoline (X = F) or the corre sponding halobenzene, nsp. [B(C6H5)(s)pc] is prepared from phthalonitrile a nd tetraphenylborate or tetraphenyloboron oxide, rasp. [B(OR)(s)pc] (R = H, CH(CH3)(2), C(CH3)(3), C6H5) is synthesized by bromide substitution of [B( Br)(s)pc] in pyridine/HOR. Substitution of [B(Br)(s)pc] in carboxylic acids yields [B(OOCR)(s)pc] (R = H, CX3 (X = H, Cl, Fl, CH2X (X = Cl, C6H5), C6H 5). All subphthalocyaninates are characterized electrochemically and by UV- VIS, IR/FIR, resonance Raman, and H-1/B-10-NMR spectroscopy. Typical B-X st retching vibrations are at 622 (X = Br), 950 (CI), 1063 (F), 1096 cm(-1) (O H) as well as between 1119 and 1052 cm(-1) (OR) resp. 985 and 1028 cm(-1) ( OOCR). The difference v(C=O)-v(C-O) > 400 cm(-1) confirms the unidentate co ordination of the carboxylato ligands. According to the crystal structure a nalysis of [B(OH)(s)pc], [B(OH)(s)pc]. 2 H2O, [B(C6H5)(s)pc], [B(OC(CH3)(s) pc], [B(OOCCH3)(s)pc]. 0.5 H2O . C2H5OH and [B(OOCCH3)(s)pc] . 0.4 H2O . 1. 1 C5H5N the (s)pc ligand is concavely distorted. This saucer shaped conform ation is independent of the acido ligands and the presence of solvate. The outermost C atomes are vertically displaced in part by more than 2 Angstrom from the N-i plane. The B atom is in a distorted tetrahedral coordination geometry It is displaced by ca 0.64 Angstrom out of the N-i plane towards t he acido ligand. The average B-N distance is 1.500 Angstrom, and the B-O di stances range from 1.418(5) to 1.473(2) Angstrom.