TY - JOUR
T1 - Reactions of Transition Metal Carbonyl Dianions with (Organo)gallium Chlorides
T2 - Anionic Gallium Complexes of Chromium, Iron, and Manganese. Structure of [PPN]2{[(CO)4Fe-Ga(CH3)-Fe(CO)4]}
AU - Fischer, Roland A.
AU - Schulte, Markus M.
AU - Herdtweck, Eberhardt
AU - Mattner, Mike R.
PY - 1997
Y1 - 1997
N2 - Salt elimination reactions between the divalent transition carbonyl metalates [L(CO)nM]2- (M = Cr, Mn, Fe; L = CO, NO; n = 3, 4) and the (organo)gallium halides ClaGaR3-a (R = CH3, CH2CH3; a = 1, 2, 3) as well as the intramolecularly donor stabilized species ClGa[(CH2)3NMe2](R) (R = Cl, Me, tBu) have been studied in some detail. Novel stable anionic (organo)gallium and chlorogallium metal complexes of the types {[L(CO)nM]Ga[(CH2)3NMe2](R)} - (1-6), {[L(CO)nM]GaCl2}- (7, 8), {[L(CO)nM]Ga(Cl)(R)}- (9, 10), and {[L(CO)nM]2Ga(CH3)}2- (11-13) have been prepared in high yields and were fully characterized by means of elemental analysis, infrared v(CO) data, and NMR spectroscopy. The effect of substituents at the Ga center on the Lewis acidity was studied by temperature-dependent NMR (inversion at the N atom of the alkylamine ligand) using the compounds 1-6. The compounds 7-10 are supposed to be dimeric. The dianionic complex [PPN]2- {[(CO)4Pe-Ga(CH3)-Fe(CO)4]} (11a) was also characterized by single-crystal X-ray diffraction: monoclinic, C2/c, a = 2699.1(3) pm, b = 1411.2(2) pm, c = 2392.8(3) pm, β= 127.45(1)°, V = 7236 × 106 pm3, Z = 4, and R = 0.038 (Rw = 0.097). The diminished Lewis acidity of the compounds 1-13 is explained by an electrostatic effect, which also stabilizes low-coordinate Ga centers without steric shielding.
AB - Salt elimination reactions between the divalent transition carbonyl metalates [L(CO)nM]2- (M = Cr, Mn, Fe; L = CO, NO; n = 3, 4) and the (organo)gallium halides ClaGaR3-a (R = CH3, CH2CH3; a = 1, 2, 3) as well as the intramolecularly donor stabilized species ClGa[(CH2)3NMe2](R) (R = Cl, Me, tBu) have been studied in some detail. Novel stable anionic (organo)gallium and chlorogallium metal complexes of the types {[L(CO)nM]Ga[(CH2)3NMe2](R)} - (1-6), {[L(CO)nM]GaCl2}- (7, 8), {[L(CO)nM]Ga(Cl)(R)}- (9, 10), and {[L(CO)nM]2Ga(CH3)}2- (11-13) have been prepared in high yields and were fully characterized by means of elemental analysis, infrared v(CO) data, and NMR spectroscopy. The effect of substituents at the Ga center on the Lewis acidity was studied by temperature-dependent NMR (inversion at the N atom of the alkylamine ligand) using the compounds 1-6. The compounds 7-10 are supposed to be dimeric. The dianionic complex [PPN]2- {[(CO)4Pe-Ga(CH3)-Fe(CO)4]} (11a) was also characterized by single-crystal X-ray diffraction: monoclinic, C2/c, a = 2699.1(3) pm, b = 1411.2(2) pm, c = 2392.8(3) pm, β= 127.45(1)°, V = 7236 × 106 pm3, Z = 4, and R = 0.038 (Rw = 0.097). The diminished Lewis acidity of the compounds 1-13 is explained by an electrostatic effect, which also stabilizes low-coordinate Ga centers without steric shielding.
UR - http://www.scopus.com/inward/record.url?scp=0000147888&partnerID=8YFLogxK
U2 - 10.1021/ic9606183
DO - 10.1021/ic9606183
M3 - Article
AN - SCOPUS:0000147888
SN - 0020-1669
VL - 36
SP - 2010
EP - 2017
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 10
ER -