TY - JOUR
T1 - Organoindium Transition Metal Complexes. Synthesis and Reactivity. Structures of [(CO)4Co]2In[CH2Si(CH3)3](C4H8O), (η5-C5H5)(CO)nM-In[(CH2)3N(CH3)2]2 (M = Fe, Ni; n= 2, 1), and (μ-CO){μ-In[(CH2)3N(CH3)2]}[(η5-C5H5)(CO)Fe]2
AU - Fischer, Roland A.
AU - Herdtweck, Eberhardt
AU - Priermeier, Thomas
PY - 1994/3/1
Y1 - 1994/3/1
N2 - Novel stable and volatile organoindium transition metal complexes of the type [L(CO)nM]a[InR3-a(D)] (1-12: M = Mo, W, Mn, Re, Fe, Co, Ni; L = η5-C5H5, CO; R = CH2SiMe3, (CH2)3NMe2; D = O-, N-donor; n= 1-4; a = 1,2) have been prepared in high yields by the reaction of the alkali metlales [L(CO)nM] (Na/K) with organoindium halides InR2X (X = Cl, Br), and have been fully characterized by elemental analysis, IR, NMR, and mass spectrometry. The (3-dimethylamino)propyl-substituted alkylindium transition metal complexes are unusually stable toward ligand redistribution equilibria. Depending on the nature of the transition metal fragment, e.g. steric bulk and radical stability, compounds with transition metal to indium ratios of 1:1 and 2:1 are thermodynamically preferred. The transition metal indium bonds in these compounds were shown to be easily cleaved by electrophilic and nucleophilic attack, oxidation and photolysis. Single-crystal data are as follows. [(CO)4Co]2In[CH2Si(CH3)3](C4H8O), 1: triclinic, P1 with a = 932.1(2) pm, b = 1054.2(2) pm, c = 1257.7(3) pm, α = 80.19(2)°, β = 80.55(2)°, γ = 85.05(2)°, V = 1199 × 106 pm3, Z = 2, and R = 0.039 (Rw = 0.025). [(η5-C5H5)(CO)n]M-In[(CH2)3N(CH3)2]2 (4, M = Fe, = 2; 5, Ni; n = 1): 4, monoclinic, P21/c, with a = 1329.1(3) pm, b = 978.4(2) pm, c = 1524.8(3) pm, β = 95.53(1)°, V= 1974 × 106 pm3, Z = 4, and R = 0.032 (Rw = 0.039); 5a (T = -80 °C), monoclinic, p21/n with a = 967.4(5) pm, b = 1507.0(2) pm, c = 1332.0(5) pm, β = 103.69(2)°, V= 1887 × 106 pm3, Z = 4, and R = 0.048 (Rw = 0.030). (μ-CO){μ-In[(CH2)3N(CH3)2]}(η5-C5H5)(CO)Fe]2,12: orthorhombic, Pnma with a = 1533.0(2) pm, b = 1253.7(1) pm, c = 1007.2(1) pm, V= 1936 × 106 pm3, Z = 4, and R = 0.041 (Rw = 0.025).
AB - Novel stable and volatile organoindium transition metal complexes of the type [L(CO)nM]a[InR3-a(D)] (1-12: M = Mo, W, Mn, Re, Fe, Co, Ni; L = η5-C5H5, CO; R = CH2SiMe3, (CH2)3NMe2; D = O-, N-donor; n= 1-4; a = 1,2) have been prepared in high yields by the reaction of the alkali metlales [L(CO)nM] (Na/K) with organoindium halides InR2X (X = Cl, Br), and have been fully characterized by elemental analysis, IR, NMR, and mass spectrometry. The (3-dimethylamino)propyl-substituted alkylindium transition metal complexes are unusually stable toward ligand redistribution equilibria. Depending on the nature of the transition metal fragment, e.g. steric bulk and radical stability, compounds with transition metal to indium ratios of 1:1 and 2:1 are thermodynamically preferred. The transition metal indium bonds in these compounds were shown to be easily cleaved by electrophilic and nucleophilic attack, oxidation and photolysis. Single-crystal data are as follows. [(CO)4Co]2In[CH2Si(CH3)3](C4H8O), 1: triclinic, P1 with a = 932.1(2) pm, b = 1054.2(2) pm, c = 1257.7(3) pm, α = 80.19(2)°, β = 80.55(2)°, γ = 85.05(2)°, V = 1199 × 106 pm3, Z = 2, and R = 0.039 (Rw = 0.025). [(η5-C5H5)(CO)n]M-In[(CH2)3N(CH3)2]2 (4, M = Fe, = 2; 5, Ni; n = 1): 4, monoclinic, P21/c, with a = 1329.1(3) pm, b = 978.4(2) pm, c = 1524.8(3) pm, β = 95.53(1)°, V= 1974 × 106 pm3, Z = 4, and R = 0.032 (Rw = 0.039); 5a (T = -80 °C), monoclinic, p21/n with a = 967.4(5) pm, b = 1507.0(2) pm, c = 1332.0(5) pm, β = 103.69(2)°, V= 1887 × 106 pm3, Z = 4, and R = 0.048 (Rw = 0.030). (μ-CO){μ-In[(CH2)3N(CH3)2]}(η5-C5H5)(CO)Fe]2,12: orthorhombic, Pnma with a = 1533.0(2) pm, b = 1253.7(1) pm, c = 1007.2(1) pm, V= 1936 × 106 pm3, Z = 4, and R = 0.041 (Rw = 0.025).
UR - http://www.scopus.com/inward/record.url?scp=0001001639&partnerID=8YFLogxK
U2 - 10.1021/ic00083a017
DO - 10.1021/ic00083a017
M3 - Article
AN - SCOPUS:0001001639
SN - 0020-1669
VL - 33
SP - 934
EP - 943
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 5
ER -