Synthesis and Structures of Intramolecularly Base-Coordinated Group 15 Aryl Halides.
Four group 15 monochlorides of the type EAr(2)Cl [Ar = 2-[(dimethylamino)methyl]phenyl, 2-(Me(2)NCH(2))C(6)H(4) (C(9)H(12)N), E = Sb (4), E = Bi (5); Ar = 8-(dimethylamino)-1-naphthyl, 8-(Me(2)N)C(10)H(6) (C(12)H(12)N), E = Sb (6), E = Bi (7)] have been prepared via the salt elimination reactions of 2 equiv of either 2-(Me(2)NCH(2))C(6)H(4)Li or 8-(Me(2)N)C(10)H(6)Li with ECl(3). Four related group 15 dihalides of the type EArX(2) [Ar = 8-(Me(2)N)C(10)H(6), X = Cl, E = As, (8), E = Sb (9); Ar = 2-(Me(2)NCH(2))C(6)H(4), X = Cl, E = Bi (10); X = I, E = Bi (11)] have been prepared via the salt elimination reactions of equimolar amounts of 8-(Me(2)N)C(10)H(6)Li or 2-(Me(2)NCH(2))C(6)H(4)Li with EX(3). The X-ray crystal structures of 4-6, 8, 9, and 11 are described, and the observed trends in the degree of intramolecular coordination of the nitrogen atoms are consistent with the view that the Lewis acidity of these complexes is associated with the E-X sigma orbitals. Crystal data for 4: triclinic, space group P&onemacr;, a = 9.1483(1) Å, b = 9.4868(1) Å, c = 12.9776(2) Å, alpha = 70.614(8) degrees, beta = 85.738(9) degrees, gamma = 83.094(9) degrees, V = 1054.0(2) Å(3), Z = 2, R = 0.0420. Crystal data for 5: monoclinic, space group P2(1)/c, a = 11.9498(1) Å, b = 11.4695(1) Å, c = 13.9456(8) Å, beta = 104.536(6) degrees, V = 1850.2(3) Å(3), Z = 4, R = 0.0375. Crystal data for 6: monoclinic, space group P2(1)/n, a = 9.4991(8) Å, b = 23.455(4) Å, c = 9.726(1) Å, beta = 100.629(8) degrees, V = 2129.8(4) Å(3), Z = 4, R = 0.0406. Crystal data for 8: orthorhombic, space group P2(1)2(1)2(1), a = 9.713(3) Å, b = 9.835(4) Å, c = 13.310(3) Å, V = 1273.8(5) Å(3), Z = 4, R = 0.0695. Crystal data for 9: orthorhombic, space group P2(1)2(1)2(1), a = 9.7140(3) Å, b = 10.0196(1) Å, c = 13.444(3) Å, V = 1308.5(3) Å(3), Z = 4, R = 0.0320. Crystal data for 11: monoclinic, space group P2(1)/c, a = 7.9455(7) Å, b = 19.3949(3) Å, c = 8.6226(9) Å, beta = 93.338(9) degrees, V = 1326.5(2) Å(3), Z = 4, R = 0.0379.
Carmalt
Claire J.
CJ
Department of Chemistry & Biochemistry, The University of Texas at Austin, Austin, Texas 78712, and School of Chemistry, Cantock's Close, University of Bristol, Bristol BS8 1TS, U.K.
Cowley
Alan H.
AH
Culp
Robert D.
RD
Jones
Richard A.
RA
Kamepalli
Smuruthi
S
Norman
Nicholas C.
NC