TY - JOUR
T1 - 199Hg NMR of mercury-bridged transition metal clusters
AU - Hajela, Sharad
AU - Rosenberg, Edward
AU - Gobetto, Roberto
AU - Milone, Luciano
AU - Osella, Domenico
N1 - Funding Information:
We gratefully acknowledget he National Science Foundation (CHE8711549E.R.). the NATO Science Program (R.G. 0705/87; E.R. and L.M.) and Consigiio Nazion-ale delle Ricerche (L.M.) for support of this research.
PY - 1989/11/14
Y1 - 1989/11/14
N2 - The 199Hg NMR data for the series of complexes (μ3-η2-C2tBu)(CO)9Ru3(μ-Hg)X (X = Cl, Br, I) and (μ3-η2-C2tBu)Ru(μ3-Hg)M (M = MoC5H5(CO)3, Mn(CO)5, Re(CO)5, FeC5H5(CO)2, RuC5H5(CO)2, Co(CO)4) and the phosphine derivative P(C6H5)3(CO)8(μ3-η2-C2tBu)Ru3(μ3-Hg)MoC5H5(CO)3 are reported. The 199Hg chemical shifts vary over a relatively large range for the series (∼ 1500 ppm) with some of the mixed transition series showing the largest downfield shifts (relative to Hg(CH3)2) reported to date. The data are discussed in light of previously reported 199Hg shifts for related complexes and although there is no correlation between HgM bond lengths in this isostructural series some general correlations of the chemical shifts with the expected polarity of the HgM bond based on the reactivity of the complexes and the qualitative theory of 199Hg chemical shifts can be made. A very large variation in line width is also observed which correlates well with the expected efficiency of quadrupole relaxation mechanisms.
AB - The 199Hg NMR data for the series of complexes (μ3-η2-C2tBu)(CO)9Ru3(μ-Hg)X (X = Cl, Br, I) and (μ3-η2-C2tBu)Ru(μ3-Hg)M (M = MoC5H5(CO)3, Mn(CO)5, Re(CO)5, FeC5H5(CO)2, RuC5H5(CO)2, Co(CO)4) and the phosphine derivative P(C6H5)3(CO)8(μ3-η2-C2tBu)Ru3(μ3-Hg)MoC5H5(CO)3 are reported. The 199Hg chemical shifts vary over a relatively large range for the series (∼ 1500 ppm) with some of the mixed transition series showing the largest downfield shifts (relative to Hg(CH3)2) reported to date. The data are discussed in light of previously reported 199Hg shifts for related complexes and although there is no correlation between HgM bond lengths in this isostructural series some general correlations of the chemical shifts with the expected polarity of the HgM bond based on the reactivity of the complexes and the qualitative theory of 199Hg chemical shifts can be made. A very large variation in line width is also observed which correlates well with the expected efficiency of quadrupole relaxation mechanisms.
UR - https://www.scopus.com/pages/publications/45249125560
U2 - 10.1016/0022-328X(89)80054-3
DO - 10.1016/0022-328X(89)80054-3
M3 - Article
SN - 0022-328X
VL - 377
SP - 85
EP - 88
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1
ER -