TY - JOUR
T1 - Transition metal coordinated Al(X)L2 and Ga(X)L2 fragments
AU - Fischer, Roland A.
AU - Schulte, Markus M.
AU - Weiss, Jurij
AU - Zsolnai, Laszlo
AU - Jacobi, Albrecht
AU - Huttner, Gottfried
AU - Frenking, Gernot
AU - Boehme, Christian
AU - Vyboishchikov, Sergei F.
PY - 1998/2/18
Y1 - 1998/2/18
N2 - Carbonylmetalate dianions react in thf with the group 13 chlorides X(m)ECl(3-m)(E = Al, Ga; X = Cl, Me, Et, (i)Bu; m = 0, 1) to yield the monoanionic species [(CO)(n)M-EX(m)Cl(2-m)]- (M = Fe, Cr, Mo, W; n = 4, 5) as the primary products which could be isolated as solvent free salts after exchange with a non-coordinating cation. After addition of a chelating Lewis base, e.g., imeda, dme, and solvent exchange with dichloromethane the primary products undergo a second salt elimination reaction, yielding the neutral intermetallic systems (CO)(n)M- Ga[X(L)2] (M=Cr, Mo, W, Fe; n = 4, 5: X - Cl, Me, Et L2 = tmeda, dme, bipy, (t)Bu-dab, thf2) (1-14) and (CO)5M-Al[X(L)2] (M = Cr, Mo, W; X = Cl, Et, (i)Bu; L2 = tmeda, tmpda) (15-20, 23, 24). The chloro derivatives can be converted to the corresponding hydrido or tetrahydridoboranato species which is exemplarily shown by compounds 21 and 22. In the case of R2GaCl (R = Me, Et; 2 equiv) as starting compounds a ligand exchange reaction, generating Gar3 occurs, before the second salt elimination takes place. The new intermetallic systems were characterized by means of elemental analysis and 1R, Raman, NMR, and mass spectroscopy. The complexes (CO)5Cr-Ga[Cl(tmeda)] (2), (CO)5W-Al[Et(tmeda)] (20), and (CO)5W-Al[Cl(tmpday)] (23) are also characterized by single-crystal X-ray diffraction. Compounds 2 and 20 crystallize in the monoclinic space group P21/(n), Z = 4, 2: a = 9.059(4) Å, b = 16.084(7) Å, c = 11.835(6) Å, β = 80.6(1)°, V = 1701(1) Å3, and R = 0.037 (R(w) - 0.118). 20: a = 8.606(2) Å, b = 16.463-(6) Å, c = 12.469(4) Å, β = 93.88(2)°, V = 1762(6) Å3, and R = 0.027 (R(w) = 0.065). Complex 23 crystallizes in the orthorhombic space group Pccn, α = 23.990(6) Å, b = 9.044(3) Å, c = 15.871(4) Å, V = 3445(1) Å3, and R = 0.044 (R(w) = 0.088). Ab initio quantum chemical calculations at the MP2 level of theory of the model complexes (CO)5W-E[Cl(NH3)2] (E = B, Al, Ga, In, T1), (CO)5W- Al[H(NH3)2], (CO)5W-AlH, and (CO)5W-AlCl are reported. The group- 13 fragments E(R)L2 behave as strong σ-donors with significant acceptor capabilities. The W-E bonds rate strong semipolar covalent bonds with large ionic contributions (D(e)(calc) between 70 and 10 kcal/mol). Only the W-tl bond is comparatively weak (D(e)(calc)) = 48 kcal/mol).
AB - Carbonylmetalate dianions react in thf with the group 13 chlorides X(m)ECl(3-m)(E = Al, Ga; X = Cl, Me, Et, (i)Bu; m = 0, 1) to yield the monoanionic species [(CO)(n)M-EX(m)Cl(2-m)]- (M = Fe, Cr, Mo, W; n = 4, 5) as the primary products which could be isolated as solvent free salts after exchange with a non-coordinating cation. After addition of a chelating Lewis base, e.g., imeda, dme, and solvent exchange with dichloromethane the primary products undergo a second salt elimination reaction, yielding the neutral intermetallic systems (CO)(n)M- Ga[X(L)2] (M=Cr, Mo, W, Fe; n = 4, 5: X - Cl, Me, Et L2 = tmeda, dme, bipy, (t)Bu-dab, thf2) (1-14) and (CO)5M-Al[X(L)2] (M = Cr, Mo, W; X = Cl, Et, (i)Bu; L2 = tmeda, tmpda) (15-20, 23, 24). The chloro derivatives can be converted to the corresponding hydrido or tetrahydridoboranato species which is exemplarily shown by compounds 21 and 22. In the case of R2GaCl (R = Me, Et; 2 equiv) as starting compounds a ligand exchange reaction, generating Gar3 occurs, before the second salt elimination takes place. The new intermetallic systems were characterized by means of elemental analysis and 1R, Raman, NMR, and mass spectroscopy. The complexes (CO)5Cr-Ga[Cl(tmeda)] (2), (CO)5W-Al[Et(tmeda)] (20), and (CO)5W-Al[Cl(tmpday)] (23) are also characterized by single-crystal X-ray diffraction. Compounds 2 and 20 crystallize in the monoclinic space group P21/(n), Z = 4, 2: a = 9.059(4) Å, b = 16.084(7) Å, c = 11.835(6) Å, β = 80.6(1)°, V = 1701(1) Å3, and R = 0.037 (R(w) - 0.118). 20: a = 8.606(2) Å, b = 16.463-(6) Å, c = 12.469(4) Å, β = 93.88(2)°, V = 1762(6) Å3, and R = 0.027 (R(w) = 0.065). Complex 23 crystallizes in the orthorhombic space group Pccn, α = 23.990(6) Å, b = 9.044(3) Å, c = 15.871(4) Å, V = 3445(1) Å3, and R = 0.044 (R(w) = 0.088). Ab initio quantum chemical calculations at the MP2 level of theory of the model complexes (CO)5W-E[Cl(NH3)2] (E = B, Al, Ga, In, T1), (CO)5W- Al[H(NH3)2], (CO)5W-AlH, and (CO)5W-AlCl are reported. The group- 13 fragments E(R)L2 behave as strong σ-donors with significant acceptor capabilities. The W-E bonds rate strong semipolar covalent bonds with large ionic contributions (D(e)(calc) between 70 and 10 kcal/mol). Only the W-tl bond is comparatively weak (D(e)(calc)) = 48 kcal/mol).
UR - http://www.scopus.com/inward/record.url?scp=0032542572&partnerID=8YFLogxK
U2 - 10.1021/ja9716463
DO - 10.1021/ja9716463
M3 - 文章
AN - SCOPUS:0032542572
SN - 0002-7863
VL - 120
SP - 1237
EP - 1248
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 6
ER -