TY - JOUR
T1 - Synthesis and structure of adduct stabilized Group III metal transition metal carbonyl complexes
T2 - New examples for Fe-Ga, Fe-In, W-Al, Cr-Al and Cr-Ga bonds
AU - Fölsing, Holger
AU - Segnitz, Oliver
AU - Bossek, Ursula
AU - Merz, Klaus
AU - Winter, Manuela
AU - Fischer, Roland A.
N1 - Funding Information:
We thank the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie for their financial support. Excellent service was provided by the computer centers HRZ Heidelberg and HRZ Bochum.
PY - 2000/7/28
Y1 - 2000/7/28
N2 - The carbonylmetallate dianions Fe(CO)2-4, Cr(CO)2-5 and W(CO)2-5 react in THF with the Group III halogenides EX3 (E = Al, Ga, In; X = Cl, Br, I) and X2ER (E = Al, Ga; X = Cl R = Me, tBu). 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)4Fe-Ga(X)(tmpda)] (X = I, Me) (1 and 2), [(CO)nM-Al(X)(tmpda)] (M = Fe, W; n = 4, 5; X = Cl, tBu) (3 and 4), [(CO)4Fe-In(Br)(tmpda)] (5), [(CO)5Cr-E(Cl)(tmpda)] (E = Al, Ga) (6 and 7), [(CO)4Fe-In(Br)(pmdeta)] (8) and cationic complex [(CO)4Fe-Ga(pmdeta)]+I- (9). The new compounds were fully characterized by means of elemental analysis, IR and NMR spectroscopy. The structures of [(CO)4Fe-Ga(Me)(tmpda)] (1), [(CO)4Fe-Ga(I)(tmpda)] (2), [(CO)5W-Al(tBu)(tmpda)] (4), [(CO)4Fe-In(Br)(tmpda)] (5), [(CO)5Cr-Al(Cl)(tmpda)] (6), [(CO)4Fe-In(Br)(pmdeta)] (8) and [(CO)4Fe-Ga(pmdeta)]+I- (9) have been studied by single-crystal X-ray diffraction. Compound 1: orthorhombic space group Pnma, Z = 4. a= 13.240(16), b = 11.623(14), c = 10.316(13) Å, α = 90, β = 90, γ = 90°, V = 1588(3) Å3, and R = 0.0364 (Rw = 0.1037). Compound 2: triclinic space group P1, Z = 2. a = 8.2059(13), b = 8.2783(13), c = 14.348(2) Å, α = 75.155(3), β = 83.953(3), γ = 62.117(3)°, V = 832.7(2) Å3, and R = 0.0346 (Rw = 0.0828). Compound 4: monoclinic space group P21/n, Z = 4. a = 8.780(5), b = 14.284(4), c = 16.339(5) Å, α = 90, β= 96.91(2), γ = 90°, V= 2034.2(14) Å3, and R = 0.0577 (Rw = 0.1303). Compound 5: orthorhombic space group P212121, Z = 4. a = 7.534(3), b = 14.978(9), c = 15.192(9) Å, α = 90, β = 90, γ = 90°, V = 1714.4(16) Å3, and R = 0.0409 (Rw = 0.1363). Compound 6: monoclinic space group C2/c, Z = 10. a = 26.458(5), b = 8.998(5), c = 15.567(3) Å, α = 90, β = 115.83(5), γ = 90°, V = 3336(2) Å3, and R = 0.0343 (Rw = 0.0650). Compound 8: monoclinic space group C2/c, Z = 16. a = 30.717(7), b = 8.746(2), c = 28.677(6) Å, α = 90, β = 94.99(5), γ = 90deg;, V = 7675(3) Å3, and R = 0.0526 (Rw = 0.1591). Compound 9: monoclinic space group P21/c, Z = 4. a = 14.157(1), b = 24.395(2), c = 13.547(1) Å, α = 90, β = 97.86(2), γ = 90°, V = 4633.9(8) Å3, and R = 0.0522 (Rw = 0.1334).
AB - The carbonylmetallate dianions Fe(CO)2-4, Cr(CO)2-5 and W(CO)2-5 react in THF with the Group III halogenides EX3 (E = Al, Ga, In; X = Cl, Br, I) and X2ER (E = Al, Ga; X = Cl R = Me, tBu). 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)4Fe-Ga(X)(tmpda)] (X = I, Me) (1 and 2), [(CO)nM-Al(X)(tmpda)] (M = Fe, W; n = 4, 5; X = Cl, tBu) (3 and 4), [(CO)4Fe-In(Br)(tmpda)] (5), [(CO)5Cr-E(Cl)(tmpda)] (E = Al, Ga) (6 and 7), [(CO)4Fe-In(Br)(pmdeta)] (8) and cationic complex [(CO)4Fe-Ga(pmdeta)]+I- (9). The new compounds were fully characterized by means of elemental analysis, IR and NMR spectroscopy. The structures of [(CO)4Fe-Ga(Me)(tmpda)] (1), [(CO)4Fe-Ga(I)(tmpda)] (2), [(CO)5W-Al(tBu)(tmpda)] (4), [(CO)4Fe-In(Br)(tmpda)] (5), [(CO)5Cr-Al(Cl)(tmpda)] (6), [(CO)4Fe-In(Br)(pmdeta)] (8) and [(CO)4Fe-Ga(pmdeta)]+I- (9) have been studied by single-crystal X-ray diffraction. Compound 1: orthorhombic space group Pnma, Z = 4. a= 13.240(16), b = 11.623(14), c = 10.316(13) Å, α = 90, β = 90, γ = 90°, V = 1588(3) Å3, and R = 0.0364 (Rw = 0.1037). Compound 2: triclinic space group P1, Z = 2. a = 8.2059(13), b = 8.2783(13), c = 14.348(2) Å, α = 75.155(3), β = 83.953(3), γ = 62.117(3)°, V = 832.7(2) Å3, and R = 0.0346 (Rw = 0.0828). Compound 4: monoclinic space group P21/n, Z = 4. a = 8.780(5), b = 14.284(4), c = 16.339(5) Å, α = 90, β= 96.91(2), γ = 90°, V= 2034.2(14) Å3, and R = 0.0577 (Rw = 0.1303). Compound 5: orthorhombic space group P212121, Z = 4. a = 7.534(3), b = 14.978(9), c = 15.192(9) Å, α = 90, β = 90, γ = 90°, V = 1714.4(16) Å3, and R = 0.0409 (Rw = 0.1363). Compound 6: monoclinic space group C2/c, Z = 10. a = 26.458(5), b = 8.998(5), c = 15.567(3) Å, α = 90, β = 115.83(5), γ = 90°, V = 3336(2) Å3, and R = 0.0343 (Rw = 0.0650). Compound 8: monoclinic space group C2/c, Z = 16. a = 30.717(7), b = 8.746(2), c = 28.677(6) Å, α = 90, β = 94.99(5), γ = 90deg;, V = 7675(3) Å3, and R = 0.0526 (Rw = 0.1591). Compound 9: monoclinic space group P21/c, Z = 4. a = 14.157(1), b = 24.395(2), c = 13.547(1) Å, α = 90, β = 97.86(2), γ = 90°, V = 4633.9(8) Å3, and R = 0.0522 (Rw = 0.1334).
KW - Aluminium
KW - Gallium
KW - Group III transition metal bonds
KW - Indium
KW - X-ray single crystal structure
UR - http://www.scopus.com/inward/record.url?scp=0037755057&partnerID=8YFLogxK
U2 - 10.1016/S0022-328X(00)00279-5
DO - 10.1016/S0022-328X(00)00279-5
M3 - Article
AN - SCOPUS:0037755057
SN - 0022-328X
VL - 606
SP - 132
EP - 140
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 2
ER -