Synthesis and spectroscopic properties of elongated ruthenium dihydrogen complexes: temperature and isotope dependence of H-H distances.
Several dihydrogen complexes of ruthenium of the form [Cp/Cp*Ru(P-P)H(2)](+) (P-P = chelating diphosphine ligand) have been prepared by reaction of the corresponding neutral chloride complexes with H(2) in the presence of NaB(ArF)(4). Treatment with D(2) or T(2) gas leads to incorporation of deuterium or tritium in the dihydrogen ligand. Measurement of the resulting H-D and H-T couplings as a function of the temperature and magnetic field gives results consistent with computational studies which predict that the H-H bond distance will increase with temperature and will be significantly shortened by isotopic substitution. The degree of the observed temperature dependence is found to be a critical function of the ancillary ligand set.
Law
James K
JK
Department of Chemistry, Box 351700, University of Washington, Seattle, Washington 98195-1700, USA.
Mellows
Heather
H
Heinekey
D Michael
DM