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Ligand‐based Reduction in a Molecular Rectangle with Four Organplatinum(IV) Vertices
Author(s) -
Kavakli Cüneyt,
Schwederski Brigitte,
Fiedler Jan,
Gudat Dietrich,
Kaim Wolfgang
Publication year - 2010
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200900445
Subject(s) - rectangle , chemistry , cyclic voltammetry , ligand (biochemistry) , electron paramagnetic resonance , crystallography , stereochemistry , trifluoromethanesulfonate , molecule , electrochemistry , physics , nuclear magnetic resonance , mathematics , organic chemistry , catalysis , biochemistry , receptor , electrode , geometry
A first organoplatinum(IV)‐based molecular rectangle [{Pt(CH 3 ) 3 } 4 (μ‐η 1 :η 1 ‐bp) 2 (μ‐η 2 :η 2 ‐bpym) 2 ] 4+ with bp = 4,4′‐bipyridine and bpym = 2,2′‐bipyrimidine has been obtained as tetrakis(triflate) in analogy to [{Re(CO) 3 } 4 (μ‐η 1 :η 1 ‐bp) 2 (μ‐η 2 :η 2 ‐bpym) 2 ] 4+ , following the correspondence between the 5d 6 configured species [ fac ‐Re I (CO) 3 ] + and [ fac ‐Pt IV (CH 3 ) 3 ] + . Analytical data, 1 H and 195 Pt NMR spectroscopic as well as mass spectrometric results confirm the identity of the species. Cyclic voltammetry, EPR, and UV/Vis/NIR spectroelectrochemistry were used to investigate the sequence of reduction steps and the location of the electron uptake. Reduction involves first the bpym ligand in two 2‐electron waves and then the bp bridge in discernible one‐electron steps.