Transition metal complexes with sulfur ligands Part LVI. First metal complexes of the crown thioether bzo2-18S6 and its tertiarybutyl derivative bubzo2-18S6 with Ru, Ag, Cr, Mo, W and Fe. X-ray structure analysis of [Ru(bzo218S6)](PF6)2·2CH3NO2

Sellmann, Dieter; Neuner, Hans-Peter; Eberlein, Rainer; Moll, Matthias; Knoch, Falk

doi:10.1016/s0020-1693(00)84831-8

Cited by 14 publications

(1 citation statement)

References 21 publications

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“…The structures of 5 and 6 differ only in a slight twist of the aromatic ring relative to the sulfur atoms. The Ru−S(thioether) bond lengths in 5 and 6 [2.3396(10) and 2.3428(12) Å, respectively] are shorter than the Ru−S(thiolate) separations [2.3763(13)−2.3858(13) Å], lying in the range 2.25−2.35 Å found in the bis(mesocyclic thioether) complexes of ruthenium(II), [Ru(9S3) 2 ]Y 2 (Y = BPh 4 , OTf 32 ), [Ru(dibenzo-(18S6))](PF 6 ) 2 , and [CpRu(9S3)](PF 6 ) 2 ; a similar trend was found in the thiolate−thioether complexes 2 and 3 10b and the Cp* analogue of 5 . The Ru−S(thioether) distances in the cationic binuclear complexes ( 7 )Cl·H 2 O and ( 9 )(PF 6 ) 2 ·MeCN (2.30 Å) appear to be significantly shorter than those in the neutral complexes 5 and 6 .…”

Section: Resultsmentioning

confidence: 99%

Arene−Ruthenium Complexes of an Acyclic Thiolate−Thioether and Tridentate Thioether Derivatives Resulting from Ring-Closure Reactions

et al. 2002

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The reaction of [(eta(6)-arene)RuCl(2)](2) (arene = C(6)Me(6), 1,4-MeC(6)H(4)CHMe(2)) with a large excess of the dianion of bis(2-mercaptoethyl) sulfide, (HSCH(2)CH(2))(2)S, obtained from deprotonation of the dithiol with freshly prepared NaOMe, gives the deep red, monomeric complexes [(eta(6)-arene)Ru(eta(3)-C(4)H(8)S(3))] (arene = C(6)Me(6) (5), 1,4-MeC(6)H(4)CHMe(2) (6)) in which the dianion is bound to the metal atom through one thioether and two thiolate sulfur atoms. Complex 5 reacts with [(eta(6)-C(6)Me(6))RuCl(2)](2) (4) in a 2:1 mole ratio to give a quantitative yield of the chloride salt of a binuclear cation [((eta(6)-C(6)Me(6))Ru)(2)Cl(mu(2)-eta(2):eta(3)-C(4)H(8)S(3))](+) (7) in which the thiolate sulfur atoms of the [(eta(6)-C(6)Me(6))Ru(eta(3)-C(4)H(8)S(3))] group bridge to a (eta(6)-C(6)Me(6))RuCl unit. This compound is also obtained directly from the reaction of 4 with the dithiolate, if the Ru dimer is used in large excess. The binuclear complex [((eta(6)-C(6)Me(6))Ru)(2)(MeCN)(mu(2)-eta(2):eta(3)-C(4)H(8)S(3))](PF(6))(2).MeCN, (9)(PF(6))(2).MeCN, is obtained by treatment of (7)Cl with NH(4)PF(6) in acetonitrile. Protonation of 5 with HCl gave the mono- and diprotonated derivatives viz. [(eta(6)-C(6)Me(6))Ru(eta(3)-C(4)H(9)S(3))]Cl, (8)Cl, and [(eta(6)-C(6)Me(6))Ru(eta(3)-C(4)H(10)S(3))]Cl(2), (10)Cl(2), respectively. The reaction of 5 with methyl iodide gives both the mono- and di-S-methylated derivatives. Treatment of 5 with dibromoalkanes, Br(CH(2))(n)Br (n = 1-5), effects ring closure to give the (eta(6)-C(6)Me(6))Ru dications containing the trithia mesocyclic zS3 (z = 8-12) ligands, isolated as their PF(6) salts. The X-ray crystal structures of 5, 6, the solvates of (7)Cl and (9)(PF(6))(2), and the trithia mesocyclic Ru complexes (eta(6)-C(6)Me(6))Ru(zS3)(PF(6))(2) (z = 8-11) are reported.

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Section: Resultsmentioning

confidence: 99%

Arene−Ruthenium Complexes of an Acyclic Thiolate−Thioether and Tridentate Thioether Derivatives Resulting from Ring-Closure Reactions

et al. 2002

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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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ChemInform Abstract: Transition Metal Complexes with Sulfur Ligands. Part 56. First Metal Complexes of the Crown Thioether bzo2‐18S6 and Its Tertiary Butyl Derivative bubzo2‐18S6 with Ru, Ag, Cr, Mo, W and Fe. X‐Ray Structure Analysis of (Ru(bzo2‐18S6))(PF6)2×2 CH3NO2.

et al. 1991

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Transition metal complexes with sulfur ligands Part LVI. First metal complexes of the crown thioether bzo2-18S6 and its tertiarybutyl derivative bubzo2-18S6 with Ru, Ag, Cr, Mo, W and Fe. X-ray structure analysis of [Ru(bzo218S6)](PF6)2·2CH3NO2

Cited by 14 publications

References 21 publications

Arene−Ruthenium Complexes of an Acyclic Thiolate−Thioether and Tridentate Thioether Derivatives Resulting from Ring-Closure Reactions

Arene−Ruthenium Complexes of an Acyclic Thiolate−Thioether and Tridentate Thioether Derivatives Resulting from Ring-Closure Reactions

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

ChemInform Abstract: Transition Metal Complexes with Sulfur Ligands. Part 56. First Metal Complexes of the Crown Thioether bzo2‐18S6 and Its Tertiary Butyl Derivative bubzo2‐18S6 with Ru, Ag, Cr, Mo, W and Fe. X‐Ray Structure Analysis of (Ru(bzo2‐18S6))(PF6)2×2 CH3NO2.

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