TY - JOUR
T1 - Aryldiazo Complexes. Structure of an Iron-Aryldiazo Complex, [Fe(CO)2(N2C6H5)(P(C6H5)3)2][BF4]
AU - Haymore, Barry L.
AU - Ibers, James A.
PY - 1975/6/1
Y1 - 1975/6/1
N2 - The structure of [Fe(CO)2(N2C6H5)(P(C6H5)3)2] [BF4] has been determined crystallographically. The compound crystallizes from acetone as solvent-free crystals in space group C2h5-P21/c with a = 13.447 (4) Å, b = 14.260 (4) Å, c = 22.755 (16) Å, β = 113.29 (2)°, Z = 4, pexptl = 1.37(1) g/cm3, and pealed = 1.373 g/cm3. Based on 3159 unique reflections with Fo2 > 3σ (Fo2), the structure was solved and refined by full-matrix, least-squares methods to R = 0.064 and Rw= 0.088. The structure consists of discrete cations and anions; the BF4 anions are partially disordered. The iron cation is five-coordinate with a coordination geometry close to trigonal bipyramidal. Apparently for steric reasons, the two carbonyl groups are nonequivalent. The phenyldiazo ligand in this complex is singly bent with Fe-N = 1.702 (6) Å, N-N = 1.201 (7) Å, N-C = 1.404 (8) Å, Fe-N-N = 179.2 (5)°, and N-N-C = 124.2 (6)°. The short Fe-N and N-N distances, as well as the general ligand geometry, suggest that multiple metal-nitrogen and nitrogen-nitrogen bonding is present and that the complex is best described as a PhN2+ complex of Fe(0). Structural and spectroscopic data suggest that the aryldiazo ligand is a good π acceptor but a poor σ donor.
AB - The structure of [Fe(CO)2(N2C6H5)(P(C6H5)3)2] [BF4] has been determined crystallographically. The compound crystallizes from acetone as solvent-free crystals in space group C2h5-P21/c with a = 13.447 (4) Å, b = 14.260 (4) Å, c = 22.755 (16) Å, β = 113.29 (2)°, Z = 4, pexptl = 1.37(1) g/cm3, and pealed = 1.373 g/cm3. Based on 3159 unique reflections with Fo2 > 3σ (Fo2), the structure was solved and refined by full-matrix, least-squares methods to R = 0.064 and Rw= 0.088. The structure consists of discrete cations and anions; the BF4 anions are partially disordered. The iron cation is five-coordinate with a coordination geometry close to trigonal bipyramidal. Apparently for steric reasons, the two carbonyl groups are nonequivalent. The phenyldiazo ligand in this complex is singly bent with Fe-N = 1.702 (6) Å, N-N = 1.201 (7) Å, N-C = 1.404 (8) Å, Fe-N-N = 179.2 (5)°, and N-N-C = 124.2 (6)°. The short Fe-N and N-N distances, as well as the general ligand geometry, suggest that multiple metal-nitrogen and nitrogen-nitrogen bonding is present and that the complex is best described as a PhN2+ complex of Fe(0). Structural and spectroscopic data suggest that the aryldiazo ligand is a good π acceptor but a poor σ donor.
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U2 - 10.1021/ic50148a033
DO - 10.1021/ic50148a033
M3 - Article
AN - SCOPUS:0039539914
SN - 0020-1669
VL - 14
SP - 1369
EP - 1376
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 6
ER -