TY - JOUR
T1 - (Electrochemical) Properties and Computational Investigations of Ferrocenyl-substituted Fe3(μ3-PFc)2(CO)9 and Co4(μ4-PFc)2(CO)9 Clusters and Their Reduced Species
AU - Korb, Marcus
AU - Liu, Xianming
AU - Walz, Sebastian
AU - Rosenkranz, Marco
AU - Dmitrieva, Evgenia
AU - Popov, Alexey A.
AU - Lang, Heinrich
PY - 2020/5/4
Y1 - 2020/5/4
N2 - The formation of ferrocenyl-functionalized iron and cobalt carbonyl clusters is reported, based on a reaction of FcPCl2 (3) (Fc = Fe(η5-C5H5)(η5-C5H4)) with Fe2(CO)9 and Co2(CO)8, respectively. Therein, nido-Fe3(CO)9(μ3-PFc)2 (4) and nido-Co4(CO)10(μ3-PFc)2 (5) clusters were obtained as the first diferrocenyl-substituted carbonyl clusters with a symmetrical cluster core. Cluster 4 shows two reversible one-electron processes within the anodic region, based on Fc/Fc+ redox events, as well as two processes in the cathodic region. In situ IR and electron paramagnetic resonance (EPR) measurements of all electronic states confirmed an Fc-based oxidation and a core-based reduction. On the basis of the results of a single-crystal X-ray analysis of structures of 4 and 5, computational studies of the highest occupied molecular orbital-lowest unoccupied molecular orbital energies, the spin density, quantum theory of atom-in-molecule delocalization indices, and the atomic charges were performed to explain the experimental results. The latter revealed a reorganization of the cluster core upon reduction and the existence of weak P···P interactions in 4 and 5. Ferrocenyl-related redox processes, occurring reversibly in case of 4, were absent for 5, due to a different distribution of the HOMO energies. EPR measurements furthermore confirmed the core-based radical anion and the formation of a decomposition product at potentials lower than [M]2- (M = Fe, Co).
AB - The formation of ferrocenyl-functionalized iron and cobalt carbonyl clusters is reported, based on a reaction of FcPCl2 (3) (Fc = Fe(η5-C5H5)(η5-C5H4)) with Fe2(CO)9 and Co2(CO)8, respectively. Therein, nido-Fe3(CO)9(μ3-PFc)2 (4) and nido-Co4(CO)10(μ3-PFc)2 (5) clusters were obtained as the first diferrocenyl-substituted carbonyl clusters with a symmetrical cluster core. Cluster 4 shows two reversible one-electron processes within the anodic region, based on Fc/Fc+ redox events, as well as two processes in the cathodic region. In situ IR and electron paramagnetic resonance (EPR) measurements of all electronic states confirmed an Fc-based oxidation and a core-based reduction. On the basis of the results of a single-crystal X-ray analysis of structures of 4 and 5, computational studies of the highest occupied molecular orbital-lowest unoccupied molecular orbital energies, the spin density, quantum theory of atom-in-molecule delocalization indices, and the atomic charges were performed to explain the experimental results. The latter revealed a reorganization of the cluster core upon reduction and the existence of weak P···P interactions in 4 and 5. Ferrocenyl-related redox processes, occurring reversibly in case of 4, were absent for 5, due to a different distribution of the HOMO energies. EPR measurements furthermore confirmed the core-based radical anion and the formation of a decomposition product at potentials lower than [M]2- (M = Fe, Co).
UR - http://www.scopus.com/inward/record.url?scp=85084225548&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.0c00276
DO - 10.1021/acs.inorgchem.0c00276
M3 - Article
C2 - 32323982
AN - SCOPUS:85084225548
SN - 0020-1669
VL - 59
SP - 6147
EP - 6160
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 9
ER -