Kristallstruktur von (Me4N)3[Ir(SCN)6], Schwingungsspektrum und Normalkoordinatenanalyse

Rohde, Jan-Uwe; Preetz, W.

doi:10.1002/(sici)1521-3749(199808)624:8<1319::aid-zaac1319>3.0.co;2-q

Cited by 9 publications

(11 citation statements)

References 8 publications

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“…Bei Winkeln von 0, 5, 10 oder 20°ergeben sich fu È r die vierfach koordinierten Palladate(II) und Platinate(II) so starke Kopplungen zwischen den Deformations-moden, insbesondere auch mit d MEC , daû diese nicht mehr sicher zugeordnet werden ko È nnen. Øhnliche Probleme sind ku È rzlich fu È r Bromorhodanoiridate(III) und [Ir(SCN) 6 ] 3± diskutiert worden [25,26]. In diesem Zusammenhang sei auf die in allen vier Komplexen in der Na È he von 330 cm ±1 zu beobachtende IR-Bande hingewiesen, die zur Zeit nicht erkla È rt werden kann.…”

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Kristallstrukturen, spektroskopische Charakterisierung und Normalkoordinatenanalyse von (n-Bu4N)2[M(ECN)4] (M = Pd, Pt; E = S, Se)

Rohde

Malottki

Preetz

2000

Z. anorg. allg. Chem.

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Die in wäßrigen Lösungen von (NH4)2[PdCl4] oder K2[PtCl4] mit KSCN oder KSeCN gebildeten Komplexanionen [Pd(SCN)4]2–, [Pt(SCN)4]2– und [Pt(SeCN)4]2– werden mit (n‐Bu4N)HSO4 in die (n‐Bu4N)‐Salze überführt. (n‐Bu4N)2[Pd(SeCN)4] wird durch Umsetzung von (n‐Bu4N)2[PdCl4] mit (n‐Bu4N)SeCN in Aceton dargestellt. Röntgenstrukturanalysen an Einkristallen von (n‐Bu4N)2[Pd(SCN)4] (monoklin, Raumgruppe P21/n, a = 13,088(3), b = 12,481(2), c = 13,574(3) Å, β = 91,494(15)°, Z = 2), (n‐Bu4N)2[Pd(SeCN)4] (monoklin, Raumgruppe P21/n, a = 13,171(2), b = 12,644(2), c = 13,560(2) Å, β = 91,430(11)°, Z = 2) und (n‐Bu4N)2[Pt(SeCN)4] (monoklin, Raumgruppe P21/n, a = 13,167(2), b = 12,641(1), c = 13,563(2) Å, β = 91,516(18)°, Z = 2) zeigen, daß die Verbindungen isotyp kristallisieren und die Komplexanionen inversionssymmetrisch und nahezu planar aufgebaut sind. Die Abstände d(Pd–S) werden mit 2,333, d(Pd–Se) mit 2,435 und 2,438 sowie d(Pt–Se) mit 2,431 und 2,432 Å ermittelt. In den Raman‐Spektren treten die Metall‐Ligand‐Valenzschwingungen von (n‐Bu4N)2[Pd(SCN)4] (1) und (n‐Bu4N)2[Pt(SCN)4] (3) im Bereich von 260–303 cm–1 sowie von (n‐Bu4N)2[Pd(SeCN)4] (2) und (n‐Bu4N)2[Pt(SeCN)4] (4) im Bereich von 171–195 cm–1 auf. Unter Verwendung der röntgenographisch ermittelten Molekülparameter lassen sich die IR‐ und Raman‐Spektren durch Normalkoordinatenanalyse zuordnen. Die Valenzkraftkonstanten betragen fd(PdS) = 1,17, fd(PdSe) = 1,17, fd(PtS) = 1,44 und fd(PtSe) = 1,42 mdyn/Å. Die 77Se‐NMR‐Resonanzen sind für 2 bei 23, für 4 bei –3 und die 195Pt‐NMR‐Resonanzen für 3 bei 549 und für 4 bei 130 ppm beobachtet worden.

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unclassified

Kristallstrukturen, spektroskopische Charakterisierung und Normalkoordinatenanalyse von (n-Bu4N)2[M(ECN)4] (M = Pd, Pt; E = S, Se)

Rohde

Malottki

Preetz

2000

Z. anorg. allg. Chem.

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“…The structural trans influence observed in the Rh III (d 6 ) complexes seems weaker when compared with that in the Re IV (d 3 ) complexes; however, it is more obvious compared with those in the complexes containing the same d 6 metal ions including Ir III and Co III . The structural trans influence in Ir III complexes can be examined by the crystal structure of ( n -Bu 4 N) 3 [Ir III (NCS)(SCN) 5 ] . The complex crystallized in the space group of P 2 1 / a including two crystallographically independent [Ir III (NCS)(SCN) 5 ] 3– complexes .…”

Section: Resultsmentioning

confidence: 99%

“…On the other hand, no obvious structural trans influence was reported for the complexes containing d 6 metal ions, Ir III and Co III . , The single crystal of ( n -Bu 4 N) 3 [Ir III (NCS)(SCN) 5 ] involves two crystallographically independent [Ir III (NCS)(SCN) 5 ] 3– moieties in a unit cell . One [Ir III (NCS)(SCN) 5 ] 3– moiety clearly shows the structural trans influence where the Ir–S bond length at the trans position of the Ir–N is slightly shorter than those at cis positions; however, the other [Ir III (NCS)(SCN) 5 ] 3– moiety has longer Ir–S at the trans position of Ir–N . Similarly, no structural trans influence was observed for the single crystals of Co III complexes, [Co III (SCN)(NH 3 ) 5 ]Cl 2 and [Co III (NCS)(NH 3 ) 5 ]Cl 2 , both of which possess virtually the same Co–N(H 3 ) bond lengths at the trans positions of Co–SCN and Co–NCS .…”

Section: Introductionmentioning

confidence: 96%

“…Single-crystal X–ray structure analyses of (isothiocyanato)(thiocyanato) complexes have been reported for [Re IV (NCS) 5 (SCN)] 2– and [Ir III (NCS)(SCN) 5 ] 3– together with the corresponding hexa(thiocyanato) complexes. , Obvious structural trans influence was observed for the Re IV (d 3 ) complex of [Re IV (NCS) 5 (SCN)] 2– , in which the bond length of Re–N at the trans position of Re–S was significantly longer than those at the cis positions . On the other hand, no obvious structural trans influence was reported for the complexes containing d 6 metal ions, Ir III and Co III . , The single crystal of ( n -Bu 4 N) 3 [Ir III (NCS)(SCN) 5 ] involves two crystallographically independent [Ir III (NCS)(SCN) 5 ] 3– moieties in a unit cell . One [Ir III (NCS)(SCN) 5 ] 3– moiety clearly shows the structural trans influence where the Ir–S bond length at the trans position of the Ir–N is slightly shorter than those at cis positions; however, the other [Ir III (NCS)(SCN) 5 ] 3– moiety has longer Ir–S at the trans position of Ir–N .…”

Section: Introductionmentioning

confidence: 99%

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Selective Crystallization of Linkage Isomers, [Rh^III(NCS)(SCN)₅]^3– and [Rh^III(SCN)₆]^3–, to Investigate Structural Trans Influence and Thermal Stability

Mukai,

Hagiwara,

Tanaka

et al. 2023

Inorg. Chem.

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Linkage isomers of homoleptic complexes, [Rh III (SCN) 6 ] 3− and [Rh III (NCS)(SCN) 5 ] 3− , formed in aqueous solution were successfully separated by employing methyltriphenylphosphonium (MePPh 3 + ) and 1-ethylquinolinium (EtQu + ) ions as countercations, respectively. The single-crystal X-ray analysis of (MePPh 3 ) 3 [Rh III (SCN) 6 ] (1) indicated that all of the SCN − ligands coordinate to the Rh III ion by S atoms with an octahedral symmetry, where the average bond length of Rh−S is 2.374(7) Å. On the other hand, the Rh III ion of (EtQu 2) is coordinated by five S atoms and one N atom of the SCN − ligands with a C 4v symmetry. Structural trans influence was observed in the shorter bond length of Rh−S at the trans position of Rh−N. The Rh−S bond length is 2.3398(13) Å significantly shorter than those of 1 by ca. 0.04 Å, although DFT calculations based on the crystal structures indicated that the effective bond order of Rh−N is higher than those of Rh−S. Thermal stability examination by thermogravimetric and differential thermal analyses (TG/DTA) and IR spectroscopy indicated that the linkage isomerization of [Rh III (SCN) 6 ] 3− to [Rh III (NCS)(SCN) 5 ] 3− proceeded after melting around 174 °C. These results clearly indicate that [Rh III (NCS)(SCN) 5 ] 3− is thermodynamically more stable than [Rh III (SCN) 6 ] 3− in solid states, although further linkage isomerization hardly occurs.

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“…Die Kristallstruktur von (Me 4 N) 3 [Ir(SCN) 6 ], das in der trigonalen Raumgruppe R3 kristallisiert, ist schon fru È her bestimmt worden [16]. Dort liegen die Tetramethylammoniumionen entsprechend dem sto È chiometrischen Verha È ltnis 3 : 1 in dreiza È hliger Anordnung komplementa È r zu den unterschiedlich ausgerichteten Thiocyanatoliganden vor.…”

Section: [Rh(secn) 6 ]unclassified

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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Kristallstruktur von (Me4N)3[Ir(SCN)6], Schwingungsspektrum und Normalkoordinatenanalyse

Cited by 9 publications

References 8 publications

Kristallstrukturen, spektroskopische Charakterisierung und Normalkoordinatenanalyse von (n-Bu4N)2[M(ECN)4] (M = Pd, Pt; E = S, Se)

Kristallstrukturen, spektroskopische Charakterisierung und Normalkoordinatenanalyse von (n-Bu4N)2[M(ECN)4] (M = Pd, Pt; E = S, Se)

Selective Crystallization of Linkage Isomers, [Rh^III(NCS)(SCN)₅]^3– and [Rh^III(SCN)₆]^3–, to Investigate Structural Trans Influence and Thermal Stability

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

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Kristallstruktur von (Me4N)3[Ir(SCN)6], Schwingungsspektrum und Normalkoordinatenanalyse

Cited by 9 publications

References 8 publications

Kristallstrukturen, spektroskopische Charakterisierung und Normalkoordinatenanalyse von (n-Bu4N)2[M(ECN)4] (M = Pd, Pt; E = S, Se)

Kristallstrukturen, spektroskopische Charakterisierung und Normalkoordinatenanalyse von (n-Bu4N)2[M(ECN)4] (M = Pd, Pt; E = S, Se)

Selective Crystallization of Linkage Isomers, [RhIII(NCS)(SCN)5]3– and [RhIII(SCN)6]3–, to Investigate Structural Trans Influence and Thermal Stability

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

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Selective Crystallization of Linkage Isomers, [Rh^III(NCS)(SCN)₅]^3– and [Rh^III(SCN)₆]^3–, to Investigate Structural Trans Influence and Thermal Stability