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Some New Dicationic Dihydrogen Complexes of Ruthenium
Author(s) -
Majumdar Kanak K.,
Nanishankar H. V.,
Jagirdar Balaji R.
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200107)2001:7<1847::aid-ejic1847>3.0.co;2-q
Subject(s) - chemistry , dihydrogen complex , protonation , ruthenium , isotopomers , nitrile , ligand (biochemistry) , nuclear magnetic resonance spectroscopy , medicinal chemistry , stereochemistry , hydride , crystallography , molecule , metal , organic chemistry , catalysis , ion , biochemistry , receptor
A series of new dicationic dihydrogen complexes of ruthenium of the type trans ‐[(dppe) 2 Ru(η 2 ‐H 2 )(RCN)][BF 4 ] 2 [dppe = Ph 2 PCH 2 CH 2 PPh 2 ; R = CH 3 , CH 3 CH 2 , CH 3 CH 2 CH 2 , CH 2 =CH, p ‐CH 3 −C 6 H 4 −CH 2 , C 6 H 5 , and (CH 3 ) 2 N] have been prepared by the protonation reaction of the precursor hydrides, trans ‐[(dppe) 2 Ru(H)(RCN)][BF 4 ] using HBF 4 ·OEt 2 . The variable temperature spin‐lattice relaxation times ( T 1 , ms) and the H, D coupling constants of the η 2 ‐HD isotopomers indicate the intact nature of the H−H bond in these complexes. It was found that the spectroscopic and chemical properties of these derivatives are not very sensitive to the change in the trans nitrile ligand. The p K a values of the dihydrogen complexes have been determined using the equilibrium: trans ‐[(dppe) 2 Ru(H)(RCN)][BF 4 ] + HBF 4 ·OEt 2 ⇄ trans ‐[(dppe) 2 Ru(η 2 ‐H 2 )(RCN)][BF 4 ] 2 + Et 2 O by 1 H NMR spectroscopy.