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Title: Synthesis and multinuclear NMR studies of (M(o-C sub 6 H sub 4 (TeMe) sub 2 )X sub 2 ) (M = Pd, Pt; X = Cl, Br, I). The presence of a characteristic ring contribution to sup 125 Te NMR chemical shifts

Abstract

The complexes (M(o-C{sub 6}H{sub 4}(TeMe){sub 2})X{sub 2}) (M = Pd, Pt; X = Cl, Br, I) and (N{sup n}Bu{sub 4})(Ir(o-C{sub 6}H{sub 4}(TeMe){sub 2})X{sub 4}) (X = Cl, Br) have been prepared, and characterized by analysis and uv-visible, ir, and multinuclear ({sup 1}H, {sup 195}Pt({sup 1}H), {sup 125}Te({sup 1}H))NMR spectroscopy. Two isomers, meso and dl invertomers, are present in each complex. The coordination shifts in the {sup 125}Te NMR spectra of the Pd and Pt complexes are compared with those reported for (M(PhTe(CH{sub 2}){sub 3}TePh)X{sub 2}) and for the analogous cis-(M(TeMePh){sub 2}x{sub 2}). It is found that, compared with the monodentate complexes, the chelate complexes having five-membered rings exhibit large high frequency coordination shifts and those having six-membered rings have small low frequency shifts. Data on complexes of o-C{sub 6}H{sub 4}(TePh){sub 2} and MeTe(CH{sub 2}){sub 3}TeMe compared with data for TePh{sub 2} and TeMe{sub 2} complexes show similar effects, which are rationalized in terms of a characteristic chelate ring contribution, defined as {Delta}{sub R}, to the shifts of the bidentate telluroethers. Similar phenomena are known for {sup 31}P and {sup 77}Se shifts in analogous complexes, but this is the first demonstration of the effect in {sup 125}Te NMR. 21 refs., 3more » figs., 4 tabs.« less

Authors:
;  [1]
  1. The University, Southampton (England)
Publication Date:
OSTI Identifier:
6944971
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (USA)
Additional Journal Information:
Journal Volume: 29:4; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AROMATICS; SYNTHESIS; CHELATES; ORGANOMETALLIC COMPOUNDS; PALLADIUM COMPLEXES; PLATINUM COMPLEXES; TELLURIUM COMPLEXES; CHEMICAL SHIFT; EXPERIMENTAL DATA; NMR SPECTRA; COMPLEXES; DATA; INFORMATION; NUMERICAL DATA; ORGANIC COMPOUNDS; SPECTRA; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties; 400202 - Isotope Effects, Isotope Exchange, & Isotope Separation

Citation Formats

Kemmitt, T, and Levason, W. Synthesis and multinuclear NMR studies of (M(o-C sub 6 H sub 4 (TeMe) sub 2 )X sub 2 ) (M = Pd, Pt; X = Cl, Br, I). The presence of a characteristic ring contribution to sup 125 Te NMR chemical shifts. United States: N. p., 1990. Web. doi:10.1021/ic00329a032.
Kemmitt, T, & Levason, W. Synthesis and multinuclear NMR studies of (M(o-C sub 6 H sub 4 (TeMe) sub 2 )X sub 2 ) (M = Pd, Pt; X = Cl, Br, I). The presence of a characteristic ring contribution to sup 125 Te NMR chemical shifts. United States. doi:10.1021/ic00329a032.
Kemmitt, T, and Levason, W. Wed . "Synthesis and multinuclear NMR studies of (M(o-C sub 6 H sub 4 (TeMe) sub 2 )X sub 2 ) (M = Pd, Pt; X = Cl, Br, I). The presence of a characteristic ring contribution to sup 125 Te NMR chemical shifts". United States. doi:10.1021/ic00329a032.
@article{osti_6944971,
title = {Synthesis and multinuclear NMR studies of (M(o-C sub 6 H sub 4 (TeMe) sub 2 )X sub 2 ) (M = Pd, Pt; X = Cl, Br, I). The presence of a characteristic ring contribution to sup 125 Te NMR chemical shifts},
author = {Kemmitt, T and Levason, W},
abstractNote = {The complexes (M(o-C{sub 6}H{sub 4}(TeMe){sub 2})X{sub 2}) (M = Pd, Pt; X = Cl, Br, I) and (N{sup n}Bu{sub 4})(Ir(o-C{sub 6}H{sub 4}(TeMe){sub 2})X{sub 4}) (X = Cl, Br) have been prepared, and characterized by analysis and uv-visible, ir, and multinuclear ({sup 1}H, {sup 195}Pt({sup 1}H), {sup 125}Te({sup 1}H))NMR spectroscopy. Two isomers, meso and dl invertomers, are present in each complex. The coordination shifts in the {sup 125}Te NMR spectra of the Pd and Pt complexes are compared with those reported for (M(PhTe(CH{sub 2}){sub 3}TePh)X{sub 2}) and for the analogous cis-(M(TeMePh){sub 2}x{sub 2}). It is found that, compared with the monodentate complexes, the chelate complexes having five-membered rings exhibit large high frequency coordination shifts and those having six-membered rings have small low frequency shifts. Data on complexes of o-C{sub 6}H{sub 4}(TePh){sub 2} and MeTe(CH{sub 2}){sub 3}TeMe compared with data for TePh{sub 2} and TeMe{sub 2} complexes show similar effects, which are rationalized in terms of a characteristic chelate ring contribution, defined as {Delta}{sub R}, to the shifts of the bidentate telluroethers. Similar phenomena are known for {sup 31}P and {sup 77}Se shifts in analogous complexes, but this is the first demonstration of the effect in {sup 125}Te NMR. 21 refs., 3 figs., 4 tabs.},
doi = {10.1021/ic00329a032},
journal = {Inorganic Chemistry; (USA)},
issn = {0020-1669},
number = ,
volume = 29:4,
place = {United States},
year = {1990},
month = {2}
}