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Synthesis, Molecular Structure and Reactions of Stable Square‐Planar 16‐Electron Ruthenium(0) Complexes: trans ‐[RuCl(NO)(PR 3 ) 2 ] ☆
Author(s) -
Flügel Ruth,
Windmüller Bettina,
Gevert Olaf,
Werner Helmut
Publication year - 1996
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19961290906
Subject(s) - ruthenium , chemistry , ligand (biochemistry) , adduct , octahedron , crystallography , stereochemistry , metal , center (category theory) , coordination geometry , medicinal chemistry , square pyramidal molecular geometry , molecule , crystal structure , catalysis , biochemistry , hydrogen bond , receptor , organic chemistry
The reduction of [RuCl 3 (NO)(PPh 3 ) 2 ] ( 1 ) with Zn/Cu generates [RuCl(NO)(PPh 3 ) 2 ] that by ligand exchange with PR 3 (R 3 i Pr 3 , i Pr 2 Ph) affords the stable 16‐electron ruthenium (0) complexes trans ‐[RuCl(NO)(PR 3 ) 2 ] ( 2, 3 ). The X‐ray structural analysis of 2 confirmed the square‐planar geometry around the metal center. HCl oxidatively adds to 2 and 3 to give the octahedral ruthenium(II) compounds [RuHCl 2 (NO)(PR 3 ) 2 ] ( 4, 5 ). On treatment of 2 and 3 with CO, TCNE, CH 2 (generated from CH 2 N 2 ) and O 2 , five‐coordinate 1:1 adducts [RuCl(NO)(L)(PR 3 ) 2 ] ( 6–12 ) are formed. The dioxygen complexes 11 and 12 react with SO 2 to afford the sulfatoruthenium(II) derivatives [RuCl(NO){η 2 ( O,O )‐O 2 SO 2 }(PR 3 ) 2 ] ( 13, 14 ). Compound 13 (R 3 P i Pr 3 ) has been characterized by X‐ray structural analysis.