Oxalate-bridged dirhenium(I) hexacarbonyl complexes: synthesis, reactions, and crystal structures |
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| Authors: | Rui Zhang Weng Kee Leong |
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| Institution: | a Natural Sciences Academic Group, National Institute of Education, Nanyang Technological University, NIE Blk 7 Science, 1 Nanyang Walk, Singapore 637616, Republic of Singapore
b Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Republic of Singapore |
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| Abstract: | The complex {Re(CO)5}2(μ,η1:η1-C2O4)] 1 undergoes thermal decarbonylation to give Re2(CO)6(C2O4)]n, which reacts with triphenylphosphine and trans-1,2-bis(diphenylphosphino)ethylene (dppene) to give anti-Re2(PPh3)2(CO)6(μ,η2:η2-C2O4)] 2 and Re2(μ-dppene)(CO)6(μ,η2:η2-C2O4)] 4, respectively. Complex 2 is oxidized on prolonged exposure to air (1 week) to form anti-Re2(OPPh3)2(CO)6(μ,η2:η2-C2O4)] 3. In the presence of excess dppene, the complex Re2(μ-dppene)2(CO)6(μ,η1:η1-C2O4)] 5 is also formed alongside 4. With the chelating diphosphine 1,3-bis(diphenylphosphino)propane (dppp), the complex (η2-dppp)Re(CO)3(μ,η1:η1-C2O4)Re(CO)3(η2-dppp)] 6 is formed. The structures of 3 and 4 have been determined by X-ray crystallography. The dppene ligand in complex 4 adopts an unusual “syn” conformation wherein the two phosphorus lone pairs of electrons are eclipsed, thus forming an “A-frame” type of bridge. |
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| Keywords: | Rhenium Carbonyl Carboxylate Oxalate Phosphine trans-1 2-Bis(diphenylphosphino)ethylene |
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