Kronenthioetherkomplexe von AgI und CuI: Die Kristallstrukturen von [{Ag3L3}{AgL2}](ClO4)4 und [LCuI] (L = 1,4,7-Trithiacyclononan)

Küppers, H.; Wieghardt, Karl; Tsay, Yi‐Hung; Nuber, Bernhard; Weiß, Johannes

doi:10.1002/ange.19870990621

Cited by 35 publications

(1 citation statement)

References 15 publications

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“…Sie besitzen polymere Struktu ren, in denen das Cu-Atom von S-und X-Atomen (X = Cl, Br, I) verzerrt tetraedrisch koordiniert ist. Die Liganden sind dabei Diethylsulfid [1], 1,3,5-Trithian [2,3], 4-Oxathian [4], 2,5-Dithiahexan [5], Tetrakis(methylthio)tetrathiafulvalen [6] und 2,3-Benzo-1,4,10,13-tetraoxa-7,16-dithiacyclooctadeca-2,3-en [7], Monomere Strukturen erhält man mit den Thiokronenethern 1,4,7-Trithia-cjc/ononan [8], 5,10,15-Trithia-cjc/o-triveratrylen [9] und 9,10,15,20-Tetrathia-c^c/o-tetraveratrylen [10,11]. Im letzten Fall tritt die für Cu(I) ungewöhn liche Koordinationszahl 5 auf.…”

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Synthese und Struktur der Basenaddukte von Kupfer(I)-Halogeniden mit Dimethylsulfid und Tetrahydrothiophen / Synthesis and Crystal Structure of Lewis Base Adducts of Copper(I)-Halides with Dimethylsulfide and Tetrahydrothiophene

Maelger

Olbrich

Kopf

et al. 1992

Zeitschrift Für Naturforschung B

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Synthese und Struktur der Basenaddukte von Kupfer(I)-Halogeniden mit Dimethylsulfid und Tetrahydrothiophen / Synthesis and Crystal Structure of Lewis Base Adducts of Copper(I)-Halides with Dimethylsulfide and Tetrahydrothiophene

Maelger

Olbrich

Kopf

et al. 1992

Zeitschrift Für Naturforschung B

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The Deprotonated Iminophosphoraneo-C6H4PPh2P=NSiMe3 as a Novel Chelating Ligand in Organocopper(I) and -zinc(II) Chemistry

Wingerter

Gornitzka

Bertrand

et al. 1999

Eur. J. Inorg. Chem.

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Lithiation of triphenyl(trimethylsilylimino)phosphorane Ph3P=NSiMe3 with MeLi gives the ortho‐metallated species [Li(o‐C6H4PPh2NSiMe3)]2·Et2O (1), which exhibits all the requirements of an organometallic ligand capable of side‐arm donation. The deprotonated ortho‐phenyl carbon atom gives access to metal–carbon σ bonds in transmetallation reactions, while the Ph2P=NSiMe3 moiety can donate to the same metal center through the imine nitrogen atom. In transmetallation reactions with CuBr, the dimeric organocopper complex [Cu(o‐C6H4PPh2NSiMe3)]2 (2) is obtained, while application of ZnCl2 yields the monomeric zinc complex [Zn(o‐C6H4PPh2NSiMe3)2] (3). Reaction with CuCl2 gives access to the new diiminophosphorane (o‐C6H4PPh2NSiMe3)2 (4) through oxidative coupling at the ortho positions. In all the metal complexes, the Ph2P=NSiMe3 residue acts as a side‐arm donating group through the nitrogen atom. The intermolecular N→Cu donor bond in 2 is as short as copper–amide bonds, while the N→Zn bond lengths in 3 are in the region normally found for donor bonds. Compound 4 is a molecule, possessing two Ph2P=NSiMe3 moieties bridged by a biphenylene group.

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Silver(I) Sandwich Complexes of Oxa‐Crowned Derivatives of Dithiomaleonitrile

1996

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The coordination chemistry of the four oxa-crowned derivatives of dithiomaleonitrile mn-12S202, mn-1 5SZO3, mn18Sz04, and mn-21S205 as well as of the acyclic bis(methy1-thio)maleonitrile mn-S2 with AgI was investigated by X-ray structural and spectroscopic methods. [6]PF6, each mn-S2 acts as a monodentate NNltnle donor. -13C-NMR studies in nitromethane solution confirm that the Ag' ions in the complexes of the mncrown dithioethers remain coordinated. However, the Ag' ion in complex of mn-S2 is decoordinated.Crown thioether metal complexes can exhibit unusual coordination numbers, redox behavior, and spectroscopic properties [']. In the 1 : 1 complexes of crown thioethers 18S6 Mixed thioethedether coordination spheres on Ag' were recently described by Blake et al. for 1 : 1 complexes with SIO crowns 15s203 (1,4,7-trioxa-10,13-dithiacyclopentadecane)[91 and 18S204 (1,4,7,10-tetraoxa-13,16-dithiacyclooctadecane)~'o~. The 1 : 1 complex with 15s203 is a S-bridged linear chain polymer of [Ag( 1 5S203)]+ units with S203Sbndg& coordination at Ag', while 1 8S204 forms a binuclear species [Ag2( 1 8S2O4)I2+ in which each Ag' is tetrahedrally coordinated by two S and two 0 atoms. Attempts to isolate a 2: 1 complex of 15S203 with Ag' failed. Metal-free macrocycles 15S203 and 18S204 adopt conformations in which the S donors lie in ex0 positions" 'I. On endocyclic complexation with Ag' the conformation of the ligands must alter dramatically and this suggests that introduction of stereochemical constraints in the form of bulky or rigid groups might enhance the endocyclic coordination possibilities of mixed S/O crowns.We synthesized the oxa-crowned derivatives of dithiomaleonitrile mn-12S202, mn-15S203, mn-1 8S204[121, and mn-21S205[131 (for ligand abbreviations see Figure 1). In contrast to those in the saturated analogues 12S202, 15S203, and 18S204['1], the sulfur atoms in the uncomplexed unsaturated macrocycles mn-12S202, mn-15S203[141, and mn-18S204[131 have restricted exodentate conformations which should enhance the formation of endocyclic complexes. This should be useful for enforcing Ag' and other metal centres into unknown thioethedether coordination spheres. In order to clarify this assumption we prepared Ag' complexes of mn-S20n+l coronands (n: 1-4) and characterised their structures by X-ray analyses and spectroscoic methods. With [Ag(rr1n-l2S~O~)~]PF~, [1JPF6, we obtained the first sandwich complex with a mixed thioethedether coordination sphere. PdC12 ['5-171, and HgC12 c~rnplexes['~~'~] of mn-crown dithioethers were recently described by us and Sibert et al.

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Kronenthioetherkomplexe von AgI und CuI: Die Kristallstrukturen von [{Ag3L3}{AgL2}](ClO4)4 und [LCuI] (L = 1,4,7-Trithiacyclononan)

Cited by 35 publications

References 15 publications

Synthese und Struktur der Basenaddukte von Kupfer(I)-Halogeniden mit Dimethylsulfid und Tetrahydrothiophen / Synthesis and Crystal Structure of Lewis Base Adducts of Copper(I)-Halides with Dimethylsulfide and Tetrahydrothiophene

Synthese und Struktur der Basenaddukte von Kupfer(I)-Halogeniden mit Dimethylsulfid und Tetrahydrothiophen / Synthesis and Crystal Structure of Lewis Base Adducts of Copper(I)-Halides with Dimethylsulfide and Tetrahydrothiophene

The Deprotonated Iminophosphoraneo-C6H4PPh2P=NSiMe3 as a Novel Chelating Ligand in Organocopper(I) and -zinc(II) Chemistry

Silver(I) Sandwich Complexes of Oxa‐Crowned Derivatives of Dithiomaleonitrile

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