199Hg NMR of mercury-bridged transition metal clusters

Sharad Hajela; Edward Rosenberg; Roberto Gobetto; Luciano Milone; Domenico Osella

doi:10.1016/0022-328X(89)80054-3

¹⁹⁹Hg NMR of mercury-bridged transition metal clusters

Sharad Hajela
, Edward Rosenberg
, Roberto Gobetto
, Luciano Milone
, Domenico Osella

Research output: Contribution to journal › Article › peer-review

Abstract

The ¹⁹⁹Hg NMR data for the series of complexes (μ₃-η²-C₂^tBu)(CO)₉Ru₃(μ-Hg)X (X = Cl, Br, I) and (μ₃-η²-C₂^tBu)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-C₂^tBu)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.

Original language	English
Pages (from-to)	85-88
Number of pages	4
Journal	Journal of Organometallic Chemistry
Volume	377
Issue number	1
DOIs	https://doi.org/10.1016/0022-328X(89)80054-3
Publication status	Published - 14 Nov 1989
Externally published	Yes

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@article{01a4ed5ac28f42279d827399a515a309,

title = "199Hg NMR of mercury-bridged transition metal clusters",

abstract = "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.",

author = "Sharad Hajela and Edward Rosenberg and Roberto Gobetto and Luciano Milone and Domenico Osella",

note = "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.",

year = "1989",

month = nov,

day = "14",

doi = "10.1016/0022-328X(89)80054-3",

language = "English",

volume = "377",

pages = "85--88",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1",

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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 -

¹⁹⁹Hg NMR of mercury-bridged transition metal clusters

Abstract

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