Phosphaniminato-Komplexe Seltener Erden. Synthese und Kristallstrukturen von [M2(C5H5)3(NPPh3)3] · 3 C7H8 mit M = Y, Dy und Er. Magnetische Eigenschaften von [Dy2(C5H5)3(NPPh3)3] · 3 C7H8

Anfang, S.; Harms, Klaus; Weller, F.; Borgmeier, O.; Lueken, Heiko; Schilder, Helmut; Dehnicke, Kurt

doi:10.1002/(sici)1521-3749(199801)624:1<159::aid-zaac159>3.0.co;2-z

Cited by 38 publications

(6 citation statements)

References 20 publications

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“…On one hand, negligible exchange coupling was found for a dimeric Dy III 2 complex bridged by two PN ligands. 35 In contrast, PN-bridged, homovalent Ni I 4 and Co I 4 complexes [36][37] displayed Curie-Weiss behavior in the temperature range of 30~150 K. 38 Taken together, these reports and the magnetometry data for 1 corroborate that bridging PN ligands can mediate strong antiferromagnetic exchange interactions with later transition metals.…”

Section: Resultsmentioning

confidence: 94%

High Spin Cobalt Complexes Supported by a Trigonal Tris(Phosphinimide) Ligand

Lee

Ciolkowski

Winslow

et al. 2021

Preprint

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Terminal, π-basic moieties occupy a prominent position in the stabilization of unusual or reactive inorganic species. The electron-releasing, π-basic properties of phosphinimides (PN) have been employed to stabilize electrondeficient early transition metals and lanthanides. In principle, a ligand field comprised of terminal PN groups should enable access to high-valent states of late first row transition metals. Herein, we report a new class of multidentate phosphinimide ligands to logically explore this hypothesis. Access to such ligands is made possible by a new procedure for the electrophilic amination of rigid, sterically-encumbering, multidentate phosphines. Such frameworks facilitate terminal PN coordination to Cobalt as demonstrated by the synthesis of a trinuclear Co II 3 complex and a homoleptic, three-coordinate Co III complex. Interestingly, the Co III complex exhibits an exceedingly rare S = 2 ground state. Combined XRD, magnetic susceptibility, and DFT studies highlight that terminally-bound PNs engage in strong dπ-pπ interactions that present a weak ligand field appropriate to stabilize high-spin states of late transition metals.the filtrate under reduced pressure. The 1 H NMR (Figure S23) matches an authentic sample of 2 (11.0 mg, 28 %). ASSOCIATED CONTENTSupporting Information. Experimental procedures and characterization. This material is available free of charge via the Internet at http://pubs.acs.org.

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Section: Resultsmentioning

confidence: 94%

High Spin Cobalt Complexes Supported by a Trigonal Tris(Phosphinimide) Ligand

Lee

Ciolkowski

Winslow

et al. 2021

Preprint

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“…Few magnetometry studies have been reported on multinuclear PN-bridged systems. On one hand, negligible exchange coupling was found for a dimeric Dy III 2 complex bridged by two PN ligands . In contrast, PN-bridged, homovalent Ni I 4 and Co I 4 complexes , exhibit well-isolated spin states attributed to the presence of direct metal–metal orbital overlap inferred by short Ni–Ni and Co–Co distances of ∼2.4 Å.…”

Section: Resultsmentioning

confidence: 96%

High Spin Cobalt Complexes Supported by a Trigonal Tris(Phosphinimide) Ligand

et al. 2021

View full text Add to dashboard Cite

Terminal, π-basic moieties occupy a prominent position in the stabilization of unusual or reactive inorganic species. The electron-releasing, π-basic properties of phosphinimides (PN) have been employed to stabilize electron-deficient early transition metals and lanthanides. In principle, a ligand field comprised of terminal PN groups should enable access to high-valent states of late first row transition metals. Herein, we report a new class of multidentate phosphinimide ligands to logically explore this hypothesis. Access to such ligands is made possible by a new procedure for the electrophilic amination of rigid, sterically encumbering, multidentate phosphines. Such frameworks facilitate terminal PN coordination to cobalt as demonstrated by the synthesis of a trinuclear CoII 3 complex and a homoleptic, three-coordinate CoIII complex. Interestingly, the CoIII complex exhibits an exceedingly rare S = 2 ground state. Combined XRD, magnetic susceptibility, and DFT studies highlight that terminally bound PNs engage in strong dπ–pπ interactions that present a weak ligand field appropriate to stabilize high-spin states of late transition metals.

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“…Heterocubanstruktur [6]. Substitutions-Reaktionen mit LiNPPh 3 lieûen sich nur unter Anwendung drastischer Bedingungen mit den Cyclopentadienid-Komplexen [LnCp 2 Br] 2 (Ln = Y, Dy, Er, Yb) erreichen [7]. Wir waren daher an der Synthese mo È glichst reiner Phosphaniminate der schwereren Alkalimetalle interessiert, zumal die auf der Basis von Phosphaniminen HNPR 3 beruhenden Verfahren wegen der Schwierigkeiten, dieses in reiner Form zu erhalten, sehr problematisch sind [8].…”

Section: Alkali Metal Phosphoraneiminates New Syntheses and Crystal unclassified

Alkalimetall-Phosphaniminate. Neue Synthesen und die Kristallstrukturen von [RbNPPh3]6 und [CsNPPh3]4

Gröb

Harms

Dehnicke

2000

Z. anorg. allg. Chem.

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Die Alkalimetall‐Phosphaniminate MNPPh3 mit M = Na, K, Rb, Cs werden durch Reaktion von Ph3PI2 mit den Alkalimetallamiden in flüssigem Ammoniak hergestellt und durch Extraktion mit Toluol in reiner Form erhalten. Das Ethylderivat KNPEt3 wird analog hierzu aus Et3PBr2 hergestellt und mit Hexan in reiner Form extrahiert. Einkristalle der Phosphaniminate von Rubidium und Caesium werden aus Toluol bzw. Toluol/Hexan erhalten und durch Kristallstrukturanalysen charakterisiert. [RbNPPh3]6 · 41/2 Toluol (1): Raumgruppe P1, Z = 2, Gitterkonstanten bei 193 K: a = 1525,5(2); b = 1902,9(2); c = 2178,3(2) pm; α = 95,435(12)°; β = 91,145(12)°; γ = 90,448(12)°; R1 = 0,0529. Die Verbindung hat die Struktur eines Doppelwürfels, dessen N‐Atome der gemeinsamen Rb2N2‐Fläche trigonal‐bipyramidal von vier Rb‐Atomen und dem P‐Atom der (NPPh3–)‐Gruppe umgeben sind. [CsNPPh3]4 · 2 Toluol · 33/4 Hexan (2 a): Raumgruppe Fd3, Z = 8, Gitterkonstanten bei 123 K: a = b = c = 2679,7(1) pm; R1 = 0,0405. [CsNPPh3]4 · 2 Toluol (2 b): Raumgruppe P21/n, Z = 4, Gitterkonstanten bei 193 K: a = 1418,9(1); b = 2258,9(1); c = 2497,6(1) pm; β = 91,055(6)°; R1 = 0,0278. Beide Caesiumverbindungen bilden Cs4N4‐Heterokubangerüste, die sich durch ihre Packung und durch die Bindungswinkel an den Cs‐ und N‐Atomen unterscheiden.

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Phosphaniminato-Komplexe Seltener Erden. Synthese und Kristallstrukturen von [M2(C5H5)3(NPPh3)3] · 3 C7H8 mit M = Y, Dy und Er. Magnetische Eigenschaften von [Dy2(C5H5)3(NPPh3)3] · 3 C7H8

Cited by 38 publications

References 20 publications

High Spin Cobalt Complexes Supported by a Trigonal Tris(Phosphinimide) Ligand

High Spin Cobalt Complexes Supported by a Trigonal Tris(Phosphinimide) Ligand

High Spin Cobalt Complexes Supported by a Trigonal Tris(Phosphinimide) Ligand

Alkalimetall-Phosphaniminate. Neue Synthesen und die Kristallstrukturen von [RbNPPh3]6 und [CsNPPh3]4

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