TY - JOUR
T1 - Competitive nucleophilic aromatic substitution and haloarene reduction in the synthesis of bimetallic π-arene Complexes
T2 - The structural characterization of [Et4N][(η6-{(CO)5W}C6H5)Cr(CO)3]
AU - Shaker, Mohammad R.
AU - Heppert, Joseph A.
AU - Thomas-Miller, M. Elizabeth
AU - Scherubel, Devin M.
AU - Takusagawa, Fusao
AU - Morgenstern, Mark A.
PY - 1989/5/1
Y1 - 1989/5/1
N2 - Collman's reagent, [Fe(CO)4]2-, reacts with (η6-ClC6H5)Cr(CO)3 to produce [(η6-{(CO)4Fe}C6H5)Cr(CO)3]− in THF/N-methyl-2-pyrrolidinone solvents, while [M(CO)5]2-(M = Cr or W) reacts with (η6-FC6H5)Cr(CO)3 in THF at 0 °C to form analogous [(η6-{(CO)5M}C6H5)Cr(CO)3]− complexes. The products are isolated as yellow-orange crystalline [Et4N]+ salts from acetone or methylene chloride and are somewhat air sensitive in both solution and the solid state. Spectroscopic data indicate that the molecules adopt a classical η6-arene structure, as opposed to the alternate possible η5-cyclohexadienide carbene valence form. This supposition is confirmed by an X-ray crystallographic study of [Et4N][(η6-{(CO)5W}C6H5)Cr(CO)3], which displays a typical W-CAr σ-bond interaction and a minimal distortion of the planarity of the arene. The reaction of [M(CO)5]2-(M = Cr or W) with (η6-ClC6H5)Cr(CO)3 results in the exhaustive reductive dehalogenation of the chlorobenzene substrate to (η6-C6H6)Cr(CO)3. This later reaction is in keeping with anticipated higher reactivity and reducing power of the [M(CO)5]2~ anions. Crystal data for [Et4N][(η6-{(CO)5W}C6H5)Cr(CO)3] at 20 °C: a = 11.599 (3) Å, b = 10.562 (2) Å, c = 20.369 (5) Å, Z = 4, Dcalcd= 1.782, space group Pca21 and R(F) = 0.0352, Rw(F) = 0.0583 for 1698 reflections.
AB - Collman's reagent, [Fe(CO)4]2-, reacts with (η6-ClC6H5)Cr(CO)3 to produce [(η6-{(CO)4Fe}C6H5)Cr(CO)3]− in THF/N-methyl-2-pyrrolidinone solvents, while [M(CO)5]2-(M = Cr or W) reacts with (η6-FC6H5)Cr(CO)3 in THF at 0 °C to form analogous [(η6-{(CO)5M}C6H5)Cr(CO)3]− complexes. The products are isolated as yellow-orange crystalline [Et4N]+ salts from acetone or methylene chloride and are somewhat air sensitive in both solution and the solid state. Spectroscopic data indicate that the molecules adopt a classical η6-arene structure, as opposed to the alternate possible η5-cyclohexadienide carbene valence form. This supposition is confirmed by an X-ray crystallographic study of [Et4N][(η6-{(CO)5W}C6H5)Cr(CO)3], which displays a typical W-CAr σ-bond interaction and a minimal distortion of the planarity of the arene. The reaction of [M(CO)5]2-(M = Cr or W) with (η6-ClC6H5)Cr(CO)3 results in the exhaustive reductive dehalogenation of the chlorobenzene substrate to (η6-C6H6)Cr(CO)3. This later reaction is in keeping with anticipated higher reactivity and reducing power of the [M(CO)5]2~ anions. Crystal data for [Et4N][(η6-{(CO)5W}C6H5)Cr(CO)3] at 20 °C: a = 11.599 (3) Å, b = 10.562 (2) Å, c = 20.369 (5) Å, Z = 4, Dcalcd= 1.782, space group Pca21 and R(F) = 0.0352, Rw(F) = 0.0583 for 1698 reflections.
UR - http://www.scopus.com/inward/record.url?scp=0000648032&partnerID=8YFLogxK
U2 - 10.1021/om00107a012
DO - 10.1021/om00107a012
M3 - Article
AN - SCOPUS:0000648032
VL - 8
SP - 1199
EP - 1206
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 5
ER -