TY - JOUR
T1 - Systematic X-ray Crystallographic Study of the Structural Manifestations of π-Donor and π-Acceptor Substituent Effects in Substituted (η6-Arene)Cr(CO)3 Complexes
AU - Hunter, Allen D.
AU - Shilliday, Lonni
AU - Furey, W. Scott
AU - Zaworotko, Michael J.
PY - 1992/4/1
Y1 - 1992/4/1
N2 - The new X-ray crystal structures of five (η6-arene)Cr(CO)3 complexes having one or two π-donor or π-acceptor substituents on their benzene rings are reported and are compared with the structures of the related (η6-arene)Cr(CO)3 complexes reported in the literature. It is found that the π-donor substituents and the ipso-carbon atoms to which they are attached are bent away from the Cr(CO)3 fragments while the π-acceptor substituents and the ipso-carbon atoms to which they are attached are approximately in the arene plane or are bent slightly toward the Cr(CO)3 fragments. The magnitudes and directions of these distortions of the arene planarity are found not to be dependent on the steric bulk of the substituent for any but the most bulky substituents. Rather, these distortions appear to be due primarily to electronic effects and a model is proposed to explain these distortions in terms of the π-donor and/or π-acceptor character of the arene substituents. The new X-ray structures reported are those of (η6-C6H5(NH2))Cr(CO)3 (C9H7CrNO3: a = 7.0425 (12) Å, b = 9.572 (4) Å, c = 7.4694 (11) Å,β= 110.798 (12)°, V = 470.7 (2) Å3; monoclinic; P21/m; Z = 2), (η6-C6H5(OMe))Cr(CO)3 (C10H8CrO4: a = 7.2485 (6) Å, b = 11.6331 (12) Å, c = 12.0276 (10) Å, V = 1014.20 (14) A3; orthorhombic; P212121; Z = 4), (η6-1,4-C6H4(NMe2)2)Cr(CO)3 (C13H16CrN2O3: a = 8.2210 (16) Å, b = 16.7202 (13) Å, c = 9.1900 (19) Å,β= 90.879 (10)°, V = 1263.1 (4) Å3; monoclinic; P21n; Z = 4), (η6-1,4-C6H4(OMe)2)Cr(CO)3 (C11H10CrO6: a = 7.859 (3) Å, b = 8.140 (9) Å, c = 19.014 (7) Å, β= 98.930 (20)°, V = 1216.5 (7) Å3; monoclinic; P21/c; Z = 4), and (η6-1,4-C6H4(CO2Me)2)Cr(CO)3 (C13H10CrO7: a = 8.8537 (14) Å, b = 20.2488 (11) Å, c = 7.5823 (12),β= 92.724 (8)°, V = 1357.8 (3) Å, monoclinic; P21/c; Z = 4).
AB - The new X-ray crystal structures of five (η6-arene)Cr(CO)3 complexes having one or two π-donor or π-acceptor substituents on their benzene rings are reported and are compared with the structures of the related (η6-arene)Cr(CO)3 complexes reported in the literature. It is found that the π-donor substituents and the ipso-carbon atoms to which they are attached are bent away from the Cr(CO)3 fragments while the π-acceptor substituents and the ipso-carbon atoms to which they are attached are approximately in the arene plane or are bent slightly toward the Cr(CO)3 fragments. The magnitudes and directions of these distortions of the arene planarity are found not to be dependent on the steric bulk of the substituent for any but the most bulky substituents. Rather, these distortions appear to be due primarily to electronic effects and a model is proposed to explain these distortions in terms of the π-donor and/or π-acceptor character of the arene substituents. The new X-ray structures reported are those of (η6-C6H5(NH2))Cr(CO)3 (C9H7CrNO3: a = 7.0425 (12) Å, b = 9.572 (4) Å, c = 7.4694 (11) Å,β= 110.798 (12)°, V = 470.7 (2) Å3; monoclinic; P21/m; Z = 2), (η6-C6H5(OMe))Cr(CO)3 (C10H8CrO4: a = 7.2485 (6) Å, b = 11.6331 (12) Å, c = 12.0276 (10) Å, V = 1014.20 (14) A3; orthorhombic; P212121; Z = 4), (η6-1,4-C6H4(NMe2)2)Cr(CO)3 (C13H16CrN2O3: a = 8.2210 (16) Å, b = 16.7202 (13) Å, c = 9.1900 (19) Å,β= 90.879 (10)°, V = 1263.1 (4) Å3; monoclinic; P21n; Z = 4), (η6-1,4-C6H4(OMe)2)Cr(CO)3 (C11H10CrO6: a = 7.859 (3) Å, b = 8.140 (9) Å, c = 19.014 (7) Å, β= 98.930 (20)°, V = 1216.5 (7) Å3; monoclinic; P21/c; Z = 4), and (η6-1,4-C6H4(CO2Me)2)Cr(CO)3 (C13H10CrO7: a = 8.8537 (14) Å, b = 20.2488 (11) Å, c = 7.5823 (12),β= 92.724 (8)°, V = 1357.8 (3) Å, monoclinic; P21/c; Z = 4).
UR - http://www.scopus.com/inward/record.url?scp=1642419780&partnerID=8YFLogxK
U2 - 10.1021/om00040a027
DO - 10.1021/om00040a027
M3 - Article
AN - SCOPUS:1642419780
SN - 0276-7333
VL - 11
SP - 1550
EP - 1560
JO - Organometallics
JF - Organometallics
IS - 4
ER -