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Synthesis, Structures, Ligand Substitution Reactions, and Electrochemistry of the Nitrile Complexes cis ‐[Ru(dppm) 2 Cl(NCR)] + PF 6 – (dppm = Bis(diphenylphosphino)methane, R = CH 3 , C 2 H 5 , t Bu, Ph)
Author(s) -
Winter Rainer F.,
Scheiring Thomas
Publication year - 2000
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/(sici)1521-3749(200005)626:5<1196::aid-zaac1196>3.0.co;2-b
Subject(s) - chemistry , nitrile , acetonitrile , pyridine , ligand (biochemistry) , electrochemistry , stereochemistry , substitution reaction , medicinal chemistry , crystal structure , crystallography , receptor , organic chemistry , electrode , biochemistry
Isomerically pure nitrile complexes cis ‐[Ru(dppm) 2 Cl(NCR)] + ( 2 a – d ) are formed upon chloride displacement from cis ‐[Ru(dppm) 2 Cl 2 ] ( 1 ) or, alternatively, by ligand substitution from the acetonitrile complex 2 a . This latter approach does also allow for the introduction of pyridine ( 3 a , b ), heptamethyldisilazane ( 4 ) or isonitrile ligands ( 5 ). All complexes are obtained as the configurationally stable cis ‐isomers. Only cis ‐[Ru(dppm) 2 Cl(CN t Bu)] + slowly isomerizes to the trans from. The solid state structures of the CH 3 CN, C 2 H 5 CN and the trans‐ t BuNC complexes were established by X‐ray crystallography. Electrochemical investigations of the nitrile complexes 2 a – d show in addition to a chemically reversible one‐electron oxidation an irrversible reduction step. In CH 2 Cl 2 solution, cis ‐ and trans ‐[Ru(dppm) 2 Cl 2 ] have been identified as the final products of the electrochemically induced reaction sequence.