TY - JOUR
T1 - Organometallic polymers with the backbone consisting of ferrocene and bimetallic tetracarboxylates
AU - Xue, Wen Mei
AU - Kühn, Fritz E.
AU - Herdtweck, Eberhardt
AU - Li, Quanchang
PY - 2001
Y1 - 2001
N2 - The tetranuclear compounds Mo2(O2CCF3)4 (FPA)2 (1), Rh2(O2CCH3)4 (FPA)2 (2), and Rh2(O2CCF3)4 (FPA)2 (3) (FPA = ferrocenyl-4-pyridylacetylene) have been synthesized by the reaction of bimetallic tetraacetates with FPA in a 1:2 stoichiometry. They have been investigated as models of oligomeric and polymeric complexes of analogous composition. UV/Vis absorption spectroscopy and cyclic voltammetry indicate that Rh2(O2CCF3)4 possesses the strongest inductive effect of the three bimetallic tetracarboxylates examined in this study. Complex 1 was additionally characterized by single crystal X-ray analysis, revealing a Mo-Mo distance of 214.22(3) pm, which is elongated in comparison to Mo2(O2CCF3)4 [209.0(4) pm], and a Mo-N distance of 250.4(2) pm. Oligomers with backbones consisting of 1,1′-bis(4-pyridylethynyl)ferrocene (BPEF) and bimetallic tetracarboxylates, [M2(O2CR)4(BPEF)]n (M = Mo, R = CF3, 4; M = Rh, R = CH3, 5; M = Rh, R = CF3, 6), have been prepared by treating the bimetallic tetracarboxylates with BPEF in a 1:1 molar ratio. The terminal groups and the number of repeating units have been estimated by elemental analyses. The oligomeric complexes 5 and 6 are insoluble in all common solvents. Complex 4 dissolves in strongly coordinating donor solvents due to replacement of the BPEF ligands by solvent molecules.
AB - The tetranuclear compounds Mo2(O2CCF3)4 (FPA)2 (1), Rh2(O2CCH3)4 (FPA)2 (2), and Rh2(O2CCF3)4 (FPA)2 (3) (FPA = ferrocenyl-4-pyridylacetylene) have been synthesized by the reaction of bimetallic tetraacetates with FPA in a 1:2 stoichiometry. They have been investigated as models of oligomeric and polymeric complexes of analogous composition. UV/Vis absorption spectroscopy and cyclic voltammetry indicate that Rh2(O2CCF3)4 possesses the strongest inductive effect of the three bimetallic tetracarboxylates examined in this study. Complex 1 was additionally characterized by single crystal X-ray analysis, revealing a Mo-Mo distance of 214.22(3) pm, which is elongated in comparison to Mo2(O2CCF3)4 [209.0(4) pm], and a Mo-N distance of 250.4(2) pm. Oligomers with backbones consisting of 1,1′-bis(4-pyridylethynyl)ferrocene (BPEF) and bimetallic tetracarboxylates, [M2(O2CR)4(BPEF)]n (M = Mo, R = CF3, 4; M = Rh, R = CH3, 5; M = Rh, R = CF3, 6), have been prepared by treating the bimetallic tetracarboxylates with BPEF in a 1:1 molar ratio. The terminal groups and the number of repeating units have been estimated by elemental analyses. The oligomeric complexes 5 and 6 are insoluble in all common solvents. Complex 4 dissolves in strongly coordinating donor solvents due to replacement of the BPEF ligands by solvent molecules.
KW - Ferrocene
KW - Molybdenum
KW - Multiple bonds
KW - Oligomers
KW - Rhodium
UR - http://www.scopus.com/inward/record.url?scp=0035177136&partnerID=8YFLogxK
U2 - 10.1002/1099-0682(20011)2001:1<213::AID-EJIC213>3.0.CO;2-Y
DO - 10.1002/1099-0682(20011)2001:1<213::AID-EJIC213>3.0.CO;2-Y
M3 - Article
AN - SCOPUS:0035177136
SN - 1434-1948
SP - 213
EP - 221
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 1
ER -