Modulation of Electronic Communication between Two Equivalent Ferrocenyl Groups Mediated Through Tricarbonylcyclobutadieneiron

Abstract

Three sets of 1,3-and 1,2-derivatives of tricarbonylcyclobutadieneiron, [Fe(CO) 3 -η 4 -CbFc 2 R 2 ] [Cb =cyclobutadiene, Fc = ferrocenyl, R = -CHO: 1a (1,3-isomer), 1b (1,2-isomer); R = -CHNOH: 2a (1,3-isomer), 2b (1,2-isomer); R = -CN: 3a (1,3isomer), 3b (1,2-isomer)] have been synthesized under facile reaction conditions starting from FcC≡C-CHO and Fe(CO) 5 . Ef-[a]

(Electrochemical) Properties and Computational Investigations of Ferrocenyl-substituted Fe3(μ3-PFc)2(CO)9and Co4(μ4-PFc)2(CO)9Clusters and Their Reduced Species

“…Both clusters exhibit similar Ct–Fe–Ct tilt angles ( 4 , 176.17(10); 5 , 176.15(3) °; Ct = centroid) and a rather eclipsed rotation of the cyclopentadienyls (<8.7(2) °). nido -Cluster 4 possesses a distorted tetragonal-pyramidal structure with Fe 2 P 2 as tetragon and an Fe­(CO) 3 moiety in the apical position, similar to Fc­(CO) 3 -capped diferrocenyl cycobutadienes …”

Triazine-Augmented Catalytic Activity of Cyclobutadiene Tricarbonyl Fe(0) Complexes for Thermal Decomposition of Ammonium Perchlorate

“…16,19a,b Consequently, Cb metal complexes are more stable than Cp/diene analogues. 16 Furthermore, functionalization of the cyclic π-systems with Cb (SiMe 3 ) 4 , 20 Cb (Admantyl) 2 , 21 Cb (Ph,TMS) 2 , 22 and Cb Fc 2 23 substituents altered the steric and electronic properties of the cyclobutadiene ligands and their tricarbonyl iron complexes. Accordingly, expanding the π-systems of Cb ligands might enhance the integration of the half-sandwich structures of CbFe(CO) 3 .…”

“…In contrast to the metal olefin π complexes, in cyclobutadiene (Cb) iron complexes, Fe-3d electrons are involved in conjugation with two lone pairs of the Cb ring and impart a 6-π-electron metallaromaticity. ,, Consequently, Cb metal complexes are more stable than Cp/diene analogues . Furthermore, functionalization of the cyclic π-systems with Cb (SiMe 3 ) 4 , Cb (Admantyl) 2 , Cb (Ph,TMS) 2 , and Cb Fc 2 substituents altered the steric and electronic properties of the cyclobutadiene ligands and their tricarbonyl iron complexes. Accordingly, expanding the π-systems of Cb ligands might enhance the integration of the half-sandwich structures of CbFe­(CO) 3 .…”