Transition metal coordinated Al(X)L2 and Ga(X)L2 fragments

Roland A. Fischer, Markus M. Schulte, Jurij Weiss, Laszlo Zsolnai, Albrecht Jacobi, Gottfried Huttner, Gernot Frenking, Christian Boehme, Sergei F. Vyboishchikov

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99 Scopus citations

Abstract

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).

Original languageEnglish
Pages (from-to)1237-1248
Number of pages12
JournalJournal of the American Chemical Society
Volume120
Issue number6
DOIs
StatePublished - 18 Feb 1998
Externally publishedYes

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