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

Allen D. Hunter, Lonni Shilliday, W. Scott Furey, Michael J. Zaworotko

Research output: Contribution to journalArticlepeer-review

Abstract

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).

Original languageEnglish
Pages (from-to)1550-1560
Number of pages11
JournalOrganometallics
Volume11
Issue number4
DOIs
Publication statusPublished - 1 Apr 1992
Externally publishedYes

Fingerprint

Dive into the research topics of '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'. Together they form a unique fingerprint.

Cite this