103Rh- und 15N-NMR-Untersuchungen an bindungsisomeren Hexakis(thiocyanato(N)-thiocyanato(S))-rhodaten(III) / 103Rh and 15N NMR Investigations on Bond Isomeric Hexakis(thiocyanato(N)-thiocyanato(S))rhodates(III)

Preetz, W.; Peters, G.; Vogt, J.

doi:10.1515/znb-1993-0314

Cited by 11 publications

(14 citation statements)

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“…Suitable techniques for ionic species are ionophoresis as a basic analytical tool 277,278 and DEAE ion exchange column chromatography for larger scale preparations of pure compounds. Through this, the series, [M(NCS) n (SCN) 6 - n ] 3- , M = Ru, n = 1−5; ,,, Rh, n = 0−4; , Os, n = 0−6; − ,, Ir, n = 0−5, have been separated into the individual linkage isomers, or in some cases, into highly enriched stereoisomers. ,,, …”

Section: B Preparation and Separationmentioning

confidence: 99%

Preparation and Spectroscopic Investigations of Mixed Octahedral Complexes and Clusters

1996

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Section: B Preparation and Separationmentioning

confidence: 99%

Preparation and Spectroscopic Investigations of Mixed Octahedral Complexes and Clusters

1996

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“…Die Se-Atome erho È hen aufgrund des sta È rker als beim Thiocyanation ausgepra È gten r-und p-Donorverhaltens die Elektronendichte am Rh-Kern, so daû [Rh(SeCN) 6 ] 3± mit d( 103 Rh) = 2287 ppm bei ho È herem Feld absorbiert als [Rh(SCN) 6 ] 3± , d( 103 Rh) = 2791 ppm [2]. 6.…”

Section: Normalkoordinatenanalyseunclassified

“…Die Synthese einiger bindungsisomerer Hexakis(thiocyanato-N-thiocyanato-S)rhodate(III) ist bereits vor einigen Jahren gelungen, und die in reiner Form isolierten Komplexe [Rh(NCS) n (SCN) 6-n ] 3± , n = 0±4, sind durch die Schwingungs-, Elektronen-, 103 Rh-und 15 N-NMR-Spektren charakterisiert worden [1,2]. Von (Ph 4 P) 3 [Rh(SCN) 6 ] liegt eine Kristallstrukturbestimmung vor [3].…”

Section: Introductionunclassified

“…Die Ro È ntgenstrukturanalyse an einem Einkristall von (Me 4 N) 3 [Rh(SeCN) 6 ] (trigonal, Raumgruppe R3, a = 14,997 (2), c = 24,437(3) A Ê , Z = 6) zeigt, daû die Verbindung isotyp zu (Me 4 N) 3 [Ir(SCN) 6 ] kristallisiert. Die Valenzkraftkonstanten betragen f d (RhSe) = 1,08 (1), 1,10 (2) und f d (RhC) = 3,14 mdyn/A Ê (2). In den Tieftemperatur-IR-und Raman-Spektren treten die Metall-Ligand-Valenzschwingungen m(RhSe) von (n-Bu 4 N) 3 [Rh(SeCN) 6 ] (1) und trans-(n-Bu 4 N) 3 [Rh(CN) 2 (SeCN) 4 ] (2) im Bereich von 170±250 cm ±1 auf.…”

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“…Die 103 Rh-NMR-Resonanzen sind fu È r 1 bei 2287, fu È r 2 bei 1680 ppm und die 77 Se-NMR-Resonanzen bei ±32,7 (1) und bei ±110,7 ppm (2) beobachtet worden. The 103 Rh NMR resonances are 2287 (1), 1680 ppm (2) and the 77 Se NMR resonances are ±32.7 (1) and ±110.7 ppm (2). 6 ] 3± and trans-[Rh(CN) 2 (SeCN) 4 ] 3± , Crystal Structure of (Me 4 N) 3 [Rh(SeCN) 6 ] Abstract.…”

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Synthese und spektroskopische Charakterisierung von [Rh(SeCN)6]3- undtrans-[Rh(CN)2(SeCN)4]3-, Kristallstruktur von (Me4N)3[Rh(SeCN)6]

Rohde

Preetz

2000

Z. anorg. allg. Chem.

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Professor Ulrich Mu È ller zum 60. Geburtstag gewidmet Inhaltsu È bersicht. Bei der Umsetzung von RhCl 3 mit KSeCN in Aceton entsteht ein Gemisch verschiedener Selenocyanatorhodate(III), aus dem [Rh(SeCN) 6 ] 3± und trans-[Rh(CN) 2 (SeCN) 4 ] 3± durch Ionenaustauschchromatographie an Diethylaminoethyl-Cellulose isoliert werden ko È nnen. Die Ro È ntgenstrukturanalyse an einem Einkristall von (Me 4 N) 3 [Rh(SeCN) 6 ] (trigonal, Raumgruppe R3, a = 14,997(2), c = 24,437(3) A Ê , Z = 6) zeigt, daû die Verbindung isotyp zu (Me 4 N) 3 [Ir(SCN) 6 ] kristallisiert. Die ausschlieûlich u È ber Se koordinierten Selenocyanatoliganden sind mit dem mittleren Rh±Se-Abstand von 2,490 A Ê und unter dem Rh±Se±C-Winkel von 104,6°gebunden. In den Tieftemperatur-IR-und Raman-Spektren treten die Metall-Ligand-Valenzschwingungen m(RhSe) von (n-Bu 4 N) 3 [Rh(SeCN) 6 ](1) und trans-(n-Bu 4 N) 3 [Rh(CN) 2 (SeCN) 4 ] (2) im Bereich von 170±250 cm ±1 auf. In 2 beobachtet man m as (CRhC) bei 479 cm ±1 . Unter Verwendung der ro È ntgenographisch ermittelten Moleku È lparameter lassen sich die Schwingungsspektren durch Normalkoordinatenanalyse zuordnen. Die Valenzkraftkonstanten betragen f d (RhSe) = 1,08 (1), 1,10 (2) und f d (RhC) = 3,14 mdyn/A Ê (2). Fu È r [Rh(SCN) 6 ] 3± , fu È r das bisher keine Berechnungen vorliegen, wird f d (RhS) = 1,32 mdyn/A Ê ermittelt. Die 103 Rh-NMR-Resonanzen sind fu È r 1 bei 2287, fu È r 2 bei 1680 ppm und die 77 Se-NMR-Resonanzen bei ±32,7 (1) und bei ±110,7 ppm (2) beobachtet worden. Die Rh±C-Bindung der Cyanoliganden in 2 wird durch ein Dublett im 13 C-NMR-Spektrum bei 136,3 ppm besta È tigt.Abstract. Treatment of RhCl 3 with KSeCN in acetone yields a mixture of selenocyanato-rhodates(III), from which [Rh(SeCN) 6 ] 3± and trans-[Rh(CN) 2 (SeCN) 4 ] 3± have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on a single crystal of (Me 4 N) 3 [Rh(SeCN) 6 ] (trigonal, space group R3, a = 14.997(2), c = 24.437(3) A Ê , Z = 6) reveals, that the compound crystallizes isotypically to (Me 4 N) 3 [Ir(SCN) 6 ]. The exclusively via Se coordinated selenocyanato ligands are bonded with the average Rh±Se distance of 2.490 A Ê and the Rh±Se±C angle of 104.6°. In the low temperature IR and Raman spectra the metal ligand stretching modes m(RhSe) of (n-Bu 4 N) 3 [Rh(SeCN) 6 ] (1) and trans-(n-Bu 4 N) 3 [Rh(CN) 2 -(SeCN) 4 ] (2) are in the range of 170±250 cm ±1 . In 2 m as (CRhC) is observed at 479 cm ±1 . The vibrational spectra are assigned by normal coordinate analysis based on the molecular parameters of the X-ray determination. The valence force constants are f d (RhSe) = 1.08 (1), 1.10 (2) and f d (RhC) = 3.14 mdyn/A Ê (2). f d (RhS) = 1.32 mdyn/A Ê is determined for [Rh(SCN) 6 ] 3± , which has not been calculated so far. The 103 Rh NMR resonances are 2287 (1), 1680 ppm (2) and the 77 Se NMR resonances are ±32.7 (1) and ±110.7 ppm (2). The Rh±C bonding of the cyano ligand in 2 is confirmed by a dublett in the 13 C NMR spectrum at 136.3 ppm.

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¹⁰³Rh NMR spectroscopy and its application to rhodium chemistry

Ernsting

Gaemers

Elsevier

2004

Magnetic Reson in Chemistry

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Rhodium is used for a number of large processes that rely on homogeneous rhodium-catalyzed reactions, for instance rhodium-catalyzed hydroformylation of alkenes, carbonylation of methanol to acetic acid and hydrodesulfurization of thiophene derivatives (in crude oil). Many laboratory applications in organometallic chemistry and catalysis involve organorhodium chemistry and a wealth of rhodium coordination compounds is known. For these and other areas, 103Rh NMR spectroscopy appears to be a very useful analytical tool. In this review, most of the literature concerning 103Rh NMR spectroscopy published from 1989 up to and including 2003 has been covered. After an introduction to several experimental methods for the detection of the insensitive 103Rh nucleus, a discussion of factors affecting the transition metal chemical shift is given. Computational aspects and calculations of chemical shifts are also briefly addressed. Next, the application of 103Rh NMR in coordination and organometallic chemistry is elaborated in more detail by highlighting recent developments in measurement and interpretation of 103Rh NMR data, in relation to rhodium-assisted reactions and homogeneous catalysis. The dependence of the 103Rh chemical shift on the ligands at rhodium in the first coordination sphere, on the complex geometry, oxidation state, temperature, solvent and concentration is treated. Several classes of compounds and special cases such as chiral rhodium compounds are reviewed. Finally, a section on scalar coupling to rhodium is provided.

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¹⁰³Rh- und ¹⁵N-NMR-Untersuchungen an bindungsisomeren Hexakis(thiocyanato(N)-thiocyanato(S))-rhodaten(III) / ¹⁰³Rh and ¹⁵N NMR Investigations on Bond Isomeric Hexakis(thiocyanato(N)-thiocyanato(S))rhodates(III)

Cited by 11 publications

References 2 publications

Preparation and Spectroscopic Investigations of Mixed Octahedral Complexes and Clusters

Preparation and Spectroscopic Investigations of Mixed Octahedral Complexes and Clusters

Synthese und spektroskopische Charakterisierung von [Rh(SeCN)6]3- undtrans-[Rh(CN)2(SeCN)4]3-, Kristallstruktur von (Me4N)3[Rh(SeCN)6]

¹⁰³Rh NMR spectroscopy and its application to rhodium chemistry

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103Rh- und 15N-NMR-Untersuchungen an bindungsisomeren Hexakis(thiocyanato(N)-thiocyanato(S))-rhodaten(III) / 103Rh and 15N NMR Investigations on Bond Isomeric Hexakis(thiocyanato(N)-thiocyanato(S))rhodates(III)

Cited by 11 publications

References 2 publications

Preparation and Spectroscopic Investigations of Mixed Octahedral Complexes and Clusters

Preparation and Spectroscopic Investigations of Mixed Octahedral Complexes and Clusters

Synthese und spektroskopische Charakterisierung von [Rh(SeCN)6]3- undtrans-[Rh(CN)2(SeCN)4]3-, Kristallstruktur von (Me4N)3[Rh(SeCN)6]

103Rh NMR spectroscopy and its application to rhodium chemistry

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¹⁰³Rh- und ¹⁵N-NMR-Untersuchungen an bindungsisomeren Hexakis(thiocyanato(N)-thiocyanato(S))-rhodaten(III) / ¹⁰³Rh and ¹⁵N NMR Investigations on Bond Isomeric Hexakis(thiocyanato(N)-thiocyanato(S))rhodates(III)

¹⁰³Rh NMR spectroscopy and its application to rhodium chemistry