SYNTHESIS AND STRUCTURES OF INTRAMOLECULARLY BASE-COORDINATED GROUP-15 ARYL HALIDES

Four group 15 monochlorides of the type EAr2Cl [Ar = 2-[(dimethylamino )methyl]phenyl, 2-(Me2NCH2)C6H4 (C9H12N), E = Sb (4), E = Bi (5); Ar = 8-(dimethylamino)-1-naphthyl, 8-(Me2N)C10H6 (C12H12N), E = Sb (6), E = Bi (4)] have been prepared via the salt elimination reactions of 2 e quiv of either 2-(Me2NCH2)C6H4Li or 8-(Me2N)C10H6Li with ECl3. Four re lated group 15 dihalides of the type EArX2 [Ar = 8-(Me2N)C10H6, X = Cl , E = As, (8), E = Sb (9); Ar = 2-(Me2NCH2)C6H4, X = Cl, E = Bi (10); X = I, E = Bi (11)] have been prepared via the salt elimination reacti ons of equimolar amounts of 8-(Me2N)C10H6Li or 2-(Me2NCH2)C6H4Li with EX3. The X-ray crystal structures of 4-6, 5, 9, and 11 are described, and the observed trends in the degree of intramolecular coordination o f the nitrogen atoms are consistent with the view that the Lewis acidi ty of these complexes is associated with the E-X sigma orbitals. Crys tal data for 4: triclinic, space group P (1) over bar, a = 9.1483(1) A ngstrom, b = 9.4868(1) Angstrom, c = 12.9776(2) Angstrom, alpha = 70.6 14(8)degrees, beta = 85.738(9)degrees, gamma = 83.094(9)degrees, V = 1 054.0(2) Angstrom(3), Z = 2, R = 0.0420. Crystal data for 5: monoclini c, space group P2(1)/c, a = 11.9498(1) Angstrom, b = 11.4695(1) Angstr om, c = 13.9456(8) Angstrom, beta = 104.536(6)degrees, V = 1850.2(3) A ngstrom(3), Z = 4, R = 0.0375. Crystal data for 6: monoclinic, space g roup P2(1)/n, a = 9.4991(5) Angstrom, b = 23.455(4) Angstrom, c = 9.72 6(1) Angstrom, beta = 100.629(8)degrees, V = 2129.8(4) Angstrom(3), Z = 4, R = 0.0406. Crystal data for 8: orthorhombic, space group P2(1)2( 1)2(1), a = 9.713(3) Angstrom, b = 9.835(4) Angstrom, c = 13.310(3) An gstrom, V = 1273.8(5) Angstrom(3), Z = 4, R = 0.0695. Crystal data for 9: orthorhombic, space group P2(1)2(1)2(1), a = 9.7140(3) Angstrom, b = 10.0196(1) Angstrom, c = 13.444(3) Angstrom, V = 1308.5(3) Angstrom (3), Z = 4, R = 0.0320. Crystal data for 11: monoclinic, space group P 2(1)/c, a = 7.9455(7) Angstrom, b = 19.3949(3) Angstrom, c = 8.6226(9) Angstrom, beta = 93.338(9)degrees, V = 1326.5(2) Angstrom(3), Z = 4, R = 0.0379.