Synthesis and structure of adduct stabilized Group III metal transition metal carbonyl complexes:: new examples for Fe-Ga, Fe-In, W-Al, Cr-Al and Cr-Ga bonds

The carbonylmetallate dianions Fe(CO)(4)(2-) Cr(CO)(5)(2-) and W(CO)(5)(2-) react in THF with the Group III halogenides EX3 (E = Al, Ga, In; X = Cl, Br, I) and X2ER (E = Al, Gal X = Cl R = Me, Bu-t). After the addition of chelating Lewis base [tmpda, pmdeta (tmpda = N,N,N',N'-tetramethylpropylenediamine, pmdeta = N,N.N',N",N"-pentamethyldiethylenetriamine)] and solvent exchange with dichloromethane, the primary products undergo a second salt elimination reaction, yielding the following complexes: [(CO)(4)Fe-Ga(X)(tmpda)] (X = 1, Me) (1 and 2), [(CO)(n)M-Al(X)(tmpda)] (M = Fe, W; n = 4, 5; X = Cl, Bu-t) (3 and 4). [(CO)(4)Fe-In(Br)(tmpda)] (5), [(CO)(5)Cr-E(Cl)(tmpda)] (E = Al, Ga) (6 and 7), [(CO)(4)Fe-In(Br)(pmdeta)] (8) and cationic complex [(CO)(4)Fe-Ga(pmdeta)]I-+(-) (9). The new compounds were fully characterized by means of elemental analysis, IR and NMR spectroscopy. The structures of [(CO)(4)Fe-Ga(Me)(tmpda)] (1), [(CO)(4)Fe-Ga(I)(tmpda)] (2), [(CO)(5)W-Al(Bu-t)(tmpda)] (4), [(Co)(4)Fe-In(Br)(tmpda)] (5), [(CO)(5)Cr-Al(Cl)(tmpda)] (6), [(CO)(4)Fe-In(Br)(pmdeta)] (8) and [(CO)(4)Fe-Ga(pmdeta)]I-+(-) (9) have been studied by single-crystal X-ray diffraction. Compound I: orthorhombic space group Pnma. Z = 4. a = 13.240(16), b = 11.623(14), c = 10.316(13) Angstrom, alpha = 90, beta = 90, gamma = 90 degrees, V = 1588(3) Angstrom(3), and R = 0.0364 (R-w = 0.1037). Compound 2: triclinic space group P (1) over bar, Z = 2. a = 8.2059(13), b = 8.2783(13), c = 14.348(2) Angstrom, alpha = 75.155(3), beta = 83.953(3), gamma = 62.117(3)degrees, V = 832.7(2) Angstrom(3), and R = 0.0346 (R-w = 0.0828). Compound 4: monoclinic space group P2(1)/n, Z = 4. a = 8.780(5), b = 14.284(4), c = 16.339(5) Angstrom, alpha = 90, beta = 96.91(2), gamma = 90 degrees, V = 2034.2(14) Angstrom(3). and R = 0.0577 (R-w = 0.1303). Compound 5. orthorhombic space group P2(1)2(1)2(1), Z = 4. a = 7.534(3). b = 14.978(9), c = 15.192(9) Angstrom, alpha = 90, beta = 90, gamma = 90 degrees, V = 17141(16) Angstrom(3), and R = 0.0409 (R-w = 01363). Compound 6: monoclinic space group C2/c, Z = 10. a = 26.458(5), b = 8.998(5), c = 15.567(3) Angstrom, alpha = 90, beta = 115.83(5), gamma = 90 degrees, V = 3336(2) Angstrom(3), and R = 0.0343 (R-w = 0.0650). Compound 8: monoclinic space group C2/c, Z = 16. a = 30.717(7), b = 8.746(2), c = 28.677(6) Angstrom, alpha = 90, beta = 94.99(5), gamma = 90 degrees, V = 7675(3) Angstrom(3), and R = 0.0526 (R-w = 0.1591). Compound 9: monoclinic space group P2(1)/c, Z = 4. a = 14.157(1), b = 24.395(2), c = 13.547(1) Angstrom, alpha = 90, beta = 97.86(2), gamma = 90 degrees, V = 4633.9(8) Angstrom(3), and R = 0.0522 (R-w = 0.1334). (C) 2000 Elsevier Science S.A. All rights reserved.