SOLUTION DYNAMICS OF THALLIUM-METAL CARBONYL-COMPOUNDS USING TL-205 NMR-SPECTROSCOPY

A Tl-205 NMR study to probe the solution structure and dynamics of a s eries of thallium-containing metal complexes has been conducted. The f ollowing compounds were examined: Tl{Co(CO)(4)}(3) (Ia), [BnMe3N](3)[T l{Fe(CO)(4)}(3)] ([BnMe3N](3)[Ib]), Tl{M(CO)(3)Cp}(3) (Ic, M = Cr; Id, M = Mo; Ie, M = W), TlFp(3) (If; Fp = CpFe(CO)(2)), [PPN](2)[Tl2Fe6(C O)(24)] ([PPN](2)[II]), [Et4N](2)[Tl2Fe4(CO)(16)] ([Et4N](2)[III]), [E t4N][L2Tl{Fe(CO)(4)}(2)] ([Et4N][IV]: [IVa](-), L-2 = bipy; [IVb](-), L-2 = en; [IVc](-), L-2 = phen; [IVd](-), L-2 = tmeda; [IVe](-), L-2 = dien), [Et4N](4)[Tl4Fe8(CO)(30)] ([Et4N](4)[V]), and TlCo(CO)(4) (VI) . The Tl-205 NMR technique was used to probe the dynamic behavior of t he Tl-metal cluster complexes [II](2-), [III](2-), and [V](4-) in solu tion and the formation of Lewis base adducts of [III](-), as well as t he possibility of formation of carbonylate anion adducts of Ia, Ic, Id , and If. [IVb](-) reacted with acetone and formed, after fortuitous o xidation, [{(CO)(4)FeL2'Tl}(2)Fe(CO)(4)] (L-2' = Me2C=NCH2CH2N=CMe2) ( VII). The initially formed complex [L-2'Tl{Fe(CO)(4)}(2)](-) ([Et4N][I Vf]) was spectroscopically characterized. Additionally, the two known but structurally uncharacterized complexes Ia and If as well as the ne w complexes [BnMe3N](3)[Ib] and VII were characterized by single-cryst al X-ray diffraction. Compound Ia crystallizes in the monoclinic space group P2(1)/n with a = 16.855(3) Angstrom, b = 6.7790(10) Angstrom, c = 19.049(4) Angstrom, beta = 113.84(3)degrees, V = 1990.8(6) Angstrom (3), Z = 4, R-1(F) = 0.0221, and wR(2)(F-2) = 0.0542 [I > 2 sigma(I)]. Compound If was synthesized from K[Fp] and TlCl3 . 4H(2)O and crystal lizes in the triclinic space group <P(1)over bar> with a = 10.789(2) A ngstrom, b = 14.239(3) Angstrom, c = 16.703(3) Angstrom, alpha = 69.39 (3)degrees, beta = 89.50(3)degrees, gamma = 69.07(3)degrees, V = 2223. 1(7) Angstrom(3), Z = 4, R-1(F) = 0.0350, and wR(2)(F-2) = 0.0877 [I > 2 sigma(I)]. Compound [BnMe3N](3)[Ib] was synthesized from Na2Fe(CO)( 4) . 3/2diox and Tl(OAc)(3) in MeCN and crystallizes in the hexagonal space group P6(3)/m with a = 18.290(3) Angstrom, c = 8.479(2) Angstrom , V = 2456.4(8) Angstrom(3), Z = 2, R-1(F) = 0.0235, and wR(2)(F-2) = 0.0494 [I > 2 sigma(I)]. Compound VII crystallizes in the triclinic sp ace group <P(1)over bar> with a = 13.597(3) Angstrom, b = 15.040(3) An gstrom, c = 10.536(2) Angstrom, alpha = 92.75(3)degrees, beta = 95.07( 3)degrees, gamma = 114.40(3)degrees, V = 1946.0(7) Angstrom(3), Z = 2, R-1(F) = 0.0461, and wR(2)(F-2) = 0.1295 [I > 2 sigma(I)].