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|a pubmed24n0500.xml
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|a (DE-627)NLM149874049
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|a (NLM)15307058
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|a DE-627
|b ger
|c DE-627
|e rakwb
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|a eng
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| 100 |
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|a Carlton, Laurence
|e verfasserin
|4 aut
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|a Rhodium-103 NMR of [Rh(X)(PPh3)3] [X = Cl, N3, NCO, NCS, N(CN)2, NCBPh3, CNBPh3, CN] and derivatives containing CO, isocyanide, pyridine, H2 and O2. Ligand, solvent and temperature effects
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|c 2004
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|a Text
|b txt
|2 rdacontent
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|a ohne Hilfsmittel zu benutzen
|b n
|2 rdamedia
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|a Band
|b nc
|2 rdacarrier
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|a Date Completed 16.03.2005
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|a Date Revised 10.12.2019
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|a published: Print
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|a Citation Status MEDLINE
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|a 2004 John Wiley & Sons, Ltd.
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|a Rhodium-103 chemical shifts are reported for 62 compounds, namely [Rh(X)(PPh3)3] [X = Cl, N3, NCO, NCS, N(CN)2, NCBPh3, CNBPh3, CN] and derivatives formed by replacement of a phosphine by CO, xylyl isocyanide (XNC) and pyridine and/or by oxidative addition of H2 or O2 to give trans-[Rh(X)(PPh3)2(CO)] (delta in the range -816 to -368 ppm) trans-[Rh(X)(PPh3)2(XNC)] (delta -817 to -250 ppm), cis-[Rh(X)(PPh3)2(py)] (the trans isomer is formed with X = CN, CNBPh3) (delta -233 to 170 ppm), [Rh(X)(H)2(PPh3)3] (delta -611 to 119), trans-[Rh(X)(H)2(PPh3)2(py)] (delta -30 to 566 ppm), [Rh(X)(O2)(PPh3)3] (delta 1393 to 3273 ppm) and cis-[Rh(X)(O2)(PPh3)2(py)] (delta 1949 to 3374 ppm). For the majority of these compounds data were obtained from solutions in chloroform and in toluene at temperatures of 247 and 300 K; for [Rh(X)(PPh3)3] (delta -562 to -4 ppm) data are reported at a number of temperatures in the range 195-300 K for solutions in chloroform, toluene and dichloromethane and at 300 K for solutions in DMSO. The expected trend to lower delta(103Rh) with decreasing temperature (vibrational shielding) is observed for the dichloromethane data, but data from solutions {of [Rh(X)(PPh3)3]} in chloroform and toluene show a number of features which diverge from this pattern, i.e. shifts to higher delta are found to accompany a decrease in temperature, most noticeably where X = CN and Cl [on changing the solvent from dichloromethane to chloroform changes in delta(103Rh) of up to 172 ppm are observed]. These results are interpreted in terms of a hydrogen-bonded interaction with the solvent that is enhanced by the presence of a polarizable ligand (CN, Cl). With a ligand (O2CCF3) that is only weakly polarizable the solvent dependence of delta(103Rh) is minimal
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|a Comparative Study
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|a Evaluation Study
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|a Journal Article
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|a Research Support, Non-U.S. Gov't
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|a Chlorine Compounds
|2 NLM
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|a Isocyanates
|2 NLM
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|a Ligands
|2 NLM
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|a Pyridines
|2 NLM
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|a Solvents
|2 NLM
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|a Carbon Monoxide
|2 NLM
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|a 7U1EE4V452
|2 NLM
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|a Hydrogen
|2 NLM
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|a 7YNJ3PO35Z
|2 NLM
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|a Rhodium
|2 NLM
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|a DMK383DSAC
|2 NLM
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|a pyridine
|2 NLM
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|a NH9L3PP67S
|2 NLM
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|a Oxygen
|2 NLM
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| 650 |
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|a S88TT14065
|2 NLM
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|i Enthalten in
|t Magnetic resonance in chemistry : MRC
|d 1985
|g 42(2004), 9 vom: 15. Sept., Seite 760-8
|w (DE-627)NLM098179667
|x 1097-458X
|7 nnns
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| 773 |
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|g volume:42
|g year:2004
|g number:9
|g day:15
|g month:09
|g pages:760-8
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|a GBV_USEFLAG_A
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|a SYSFLAG_A
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|a GBV_NLM
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|a GBV_ILN_350
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|a AR
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|d 42
|j 2004
|e 9
|b 15
|c 09
|h 760-8
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