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Matthias Moll

Friedrich-Alexander-Universität Erlangen-Nürnberg, Inorganic Chemistry, Alumnus

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Royal Botanic Gardens Kew

Dragana Filipovic

Max Planck Institute for the Science of Human History

University of Cambridge

Angel Berenguer

University of Alicante / Universidad de Alicante

Emanuela Cristiani

Università degli Studi "La Sapienza" di Roma

Dr Noore Alam Tufani

Sher-e-Kashmir University of Agricultural Sciences and Technology (SKUAST)

University of the Basque Country, Euskal Herriko Unibertsitatea

Isidro Martínez Mira

University of Alicante / Universidad de Alicante

Universiteit Leiden

Dr. Anika Niambi Al-Shura, BSc, MSOM, PhD

Independent Academic Research Studies

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Papers by Matthias Moll

Übergangsmetallkomplexe mit Schwefelliganden, XCl+ Fell-Komplexe des fünfzähnigen Thioether-Thiolat-Aminliganden ′buNHS4′-H2: Synthese, Charakterisierung, Reaktivität und Stereochemie (′buNHS4′-H2 = 2,2′-Bis(2-mercapto-3,5-di-tertiärbutyl-phenylthio)diethylamin) / Transition Metal Complexes with ...

Zeitschrift für Naturforschung B, Aug 1, 1992

In search o f m odel com pounds for the active centers o f nitrogenases, [Fe(L)('buN HS4')] compl... more In search o f m odel com pounds for the active centers o f nitrogenases, [Fe(L)('buN HS4')] complexes o f the pentadentate thioether-thiolate-amine ligand 'buN HS4'2-('buN HS4'-H2 = 2,2'-bis(2-mercapto-3,5-di-tertiarybutyl-phenylthio)diethylamine) were obtained. A lkylation o f 'buS2'-H2 with (BrC2H4),N H yielded the new ligand 'buN HS4'-H2 as a mixture o f positional isomers. Isolation o f single isomers was achieved by reacting the mixture with FeCl2-4 H 20 and CO in order to give the corresponding [Fe(CO)] complexes which were se parated and hydrolyzed to yield the free ligands. R eaction o f 'buN HS4'-H2 with FeCl2 -4 H 20 led to the high-spin complex [Fe('buN HS4')] which is extremely air-sensitive in solution. It rapidly reacts with L = CO, NO, PM e3, and N 2H4, and is the m ost suitable starting material for syntheses o f [Fe(L)('buN HS4')l complexes which were characterized for L = CO, N O +, N O , PM e3 and N 2H4. All complexes are considerably better soluble in organic solvents than the corresponding parent compounds [Fe(L)('NHS4')], ('N hS4'-H 2 = 2,2'-bis(2-mercaptophenylthio)diethylamine), but have similar properties in most other respects. In the oxidation o f [F e(N 2H 4)('buN HS4')] at low temperatures, there is evidence for the form ation o f the diazene com plex [u-N 2H2{Fe('buN HS4')}2].

Übergangsmetallkomplexe mit Schwefelliganden, LVIII / Transition Metal Complexes with Sulfur Ligands, LVIII

Zeitschrift für Naturforschung B, Mar 1, 1991

In stitu t für A norganische Chem ie d er U niversität, E gerlandstraße 1, D-8520 E rlangen Z. N ... more In stitu t für A norganische Chem ie d er U niversität, E gerlandstraße 1, D-8520 E rlangen Z. N atu rfo rsch . 46b, 3 0 3 -3 0 6 (1991); eingegangen am 10. O k to b er 1990 R u thenium , C row n T hioethers, V inyl-Thioether, Sulfur Ligands T he m o no catio n [R u('S6'-C H = C H 2)]+, [2]+, ('S6'-C H = C H 2-= 2.3.11.12-dibenzo-1.4.7.10.13.16-hexathiaoctadec-17-ene(l -)) form s u n d er norm al co n d itio n s by S -C bond cleavage in an irreversible and selective reaction on treating salts o f the d ication [R u (b zo 2-18S6)]2+, [1]2+, (bzo-,-18S6 = 2 .3 .1 1.12-dibenzo-1.4.7.10.13.16-hexathiacyclooctadecane) with one equivalent o f base. T his reaction dem o n strates the drastic S -C activation in co o rd in ated thioethers and should be tak en into consideration w hen cofactors are isolated from m etal sul fur enzym es. * LVII. M itteilung s. Ref. [1], ** S ond erd ru ck an fo rd eru n g en an Prof. D r. D. Sell m ann.

Übergangsmetallkomplexe mit Schwefelliganden, LX / Transition Metal Complexes with Sulfur Ligands, LX

Zeitschrift für Naturforschung B, May 1, 1991

Transition M etal Complexes with Sulfur Ligands, LX* Synthesis, Properties and Reactivity of Isom... more Transition M etal Complexes with Sulfur Ligands, LX* Synthesis, Properties and Reactivity of Isomerically Pure [Fe(L)'buSs'] Complexes with L = CO, NO, N O +, P(OPh)3 ('buS5'2-= Dianion of 2,2'-Bis(2-mercapto-3,5-di-tertiary-butylphenylthio)diethylsulfide) Dieter Sellm ann+, Klaus Höhn und M atthias Moll In stitu t für A norganische C hem ie der U n iversität E rlan g e n -N ü rn b erg , E g erla n d straß e 1, D-8520 E rlangen Z. N atu rfo rsch . 46b, 6 6 5 -6 7 2 (1991); eingegangen am 19. N o v em b er 1990 Iron S ulfur C om plexes, Synthesis, R eactions, Stereochem istry, T ran sitio n M etal Com plexes T he p en tad e n tate th io eth er thiolate ligand 'buS5'2-(= d ian io n o f 2,2'-bis(2-m ercapto-3,5-di-tertiary-butylphenylthio)diethylsulfide) reacts w ith iro n (II) ions to give the diam agnetic [F e'buS5'] (1), which only co o rd in ates o ~n ligands such as C O , N O , N O + o r P (O P h )3. In this respect, the [F e'buS5'] fragm ent differs from the p aren t com plex [F e'S /] ('S 5'2~ = d ianion o f 2,2'-bis(2-m ercaptophenylthio)diethylsulfide) as well as from the related [F e'N HS4'] ('N HS4'2~ = dian io n o f 2,2'-bis(2-m ercaptophenylthio)diethylam ine), b o th o f which are able to co o rd in ate also rr-ligands such as N 2H 4 o r N H 3. Synthesis o f [F e(C O )'buS5'] (2), yields tw o stereoisom ers th a t can be easily separated ow ing to their different solubility.

Übergangsmetallkomplexe mit Schwefelliganden, LXXX. Synthese, Struktur, Oxotransfer- und redoxgekoppelte Kondensationsreaktionen von Molybdän-Oxo-Komplexen mit dem sterisch anspruchsvollen vierzähnigen Thioether-Thiolat-Liganden '<sup>bu</sup>S<sub>4</sub>'<sup>2-</sup> ('<sup>bu</sup>S<sub>4</su...

Zeitschrift für Naturforschung B, 1992

Transition Metal Complexes with Sulfur Ligands, LXXX* Syntheses, Structures, Oxo Transfer and Red... more Transition Metal Complexes with Sulfur Ligands, LXXX* Syntheses, Structures, Oxo Transfer and Redox Coupled Condensation Reactions o f M olybdenum Oxo Complexes with the Sterically Demanding Tetradentate Thioether-Thiolato-Ligand 'buS4'2-('bug^'2-_ i,2-Bis(2-m ercapto-3,5-di-/-butylphenylthio)ethane(2-))

Notizen: Protonierung und Alkylierung von Olefin-cyano-dicarbonyl-ferraten(0)

Zeitschrift für Naturforschung B, Aug 1, 1976

Olefin Dicarbonyl Iron(O) Isocyanic Acids, Olefin Isonitrile Dicarbonyl Iron The anionic complexe... more Olefin Dicarbonyl Iron(O) Isocyanic Acids, Olefin Isonitrile Dicarbonyl Iron The anionic complexes [olenFe(CO)2CN]~ (olen = butadiene, 1,3-cyclohexadiene, cyclooctatetraene), formed by the reaction of olenFe(CO)3 with NaN[Si(CH3)3]2, have been protonated to the isocyanic acid derivates olenFe(CO)2CNH, and alkylated with [Et30]BF4 to give the isonitrile complexes olenFe(CO)2CNEt.

Übergangsmetallkomplexe mit Schwefelliganden, XXIV* Reduktive Nitrosylierung von [MoCl2(dttd)] zu [Mo(NO)2(dttd)];Eigenschaften, Struktur und Reaktion zu NPR3-Komplexen[Mo(NO)(NPR3)dttd] (PR3=PMe3, PEt3, PMePh2, PEtPh2, PPh3;dttd2-=2,3,8,9-Dibenzo-1,4,7,10-tetrahiadecan(2-)) / Transition Metal Co...

Zeitschrift für Naturforschung B, 1986

In order to study the properties of sulfur coordinated transition metal centers. [MoCl2dttd] (dtt... more In order to study the properties of sulfur coordinated transition metal centers. [MoCl2dttd] (dttd2 = 2,3,8,9-dibenzo-1,4.7,10-tetrathiadecane(2-)) was reacted with NO in the presence of Zn. [Mo(NO)2dttd] was obtained whose X-ray structure analysis shows that Mo is coordinated pseudo-octahedrally by two trans thiolato S, two cis thioether S as well as two cis N atoms of nearly linear MoNO groups. With respect to its low v(NO) frequencies (1760/1665 cm -1) and quite normal bond lengths as well as angles [Mo(NO)2dttd] shows unexpectedly facile and rapid reactions with nucleophiles; with two equivalents of PR3 (PMe3, PEt3, PMePh2, PEtPh2, PPh3) it yields the corresponding phosphiniminato complexes [Mo(NO)(NPR3)dttd] and free phosphinoxides OPR3, respectively. Reaction mechanisms as well as the bonding situation in the [Mo(NPR3)] entity are discussed; on the basis of 95Mo and 14N NMR it is concluded that the conversion of NO into NPR3 ligands includes a reduction of N(+2) to N(-3) as we...

Übergangsmetallkomplexe mit Schwefelliganden, LXX. / Transition Metal Complexes with Sulfur Ligands, LXX

Zeitschrift für Naturforschung B, Nov 1, 1991

'S4')] IM o(i^-NH20)(N O)('S 4')]-Reduktion ('S4'2-= l,2-Bis(2-mercaptophenylthio)ethan(2-)) Tran... more

Transition-metal complexes with sulfur ligands. 45. Model reactions for oxidoreductases with metal-sulfur centers: proton-induced triphenylphosphine/hydrochloric acid exchange in [Ru(PPh3)2(L)] and properties of the resulting HCl complexes [Ru(ClH)(PPh3)(L)] (L = 1,2-bis((2-mercaptophenyl)thio)et...

Inorganic Chemistry, 1990

We discuss the influence of thiolate ligands at metal-sulfur centers, in particular with respect ... more We discuss the influence of thiolate ligands at metal-sulfur centers, in particular with respect to reactions involving protons. Aims of these investigations were the identification of the reaction products of [Ru(PPh 3 ) 2 (L)] (L= bu S 4 2- , S 4 2- ) with HCl, better insight into the reaction mechanisms, syntheses of new complexes with the [Ru(L)] fragments, and elucidation of potential bioinorganic relevances

ChemInform Abstract: Transition Metal Complexes with Sulfur Ligands. Part 31. Six‐ and Seven‐Coordinate CO, NO, PMe3 and Phosphineiminato Molybdenum Complexes with (Mo(S4)) Frameworks ((S4) = 2,3;8,9‐dibenzo‐1,4,7,10‐tetrathiadecane(2‐))

ChemInform, 1988

In order to explain the high reactivity of the Mo complex (III) towards tert. phosphines the stru... more In order to explain the high reactivity of the Mo complex (III) towards tert. phosphines the structures of the seven‐coordinate trimethylphosphinedicarbonyl complex (I) and the six‐coordinate phosphine imidato complex (II) (for both space group P21/c, Z=4) are determined by X‐ray analysis and compared to structures of analogous complexes.

ChemInform Abstract: Transition Metal Complexes with Sulfur Ligands. Part 28. Ruthenium Complexes of the Pentadentate Thioether Thiolate Ligands dpttd2‐ (2,3,11,12‐Dibenzo‐1,4,7,10,13‐pentathiatridecane(‐2)) and the Sterically Demanding Derivative tBu4‐dpttd2‐ (14,16,18,20‐Tetra(t‐butyl)‐2,3,11,1...

ChemInform, 1987

According to the scheme, the template alkylation of 1,2‐benzenedithiolate by bis(β‐bromoethyl) su... more

ChemInform Abstract: REAKTIONEN VON NA2(M2(CO)10) (M=CR,MO,W) MIT INX3 (X=CL,BR,I) UND DIE KRISTALLSTRUKTUR VON CR(CO)5INBR.THF

Chemischer Informationsdienst, 1978

Die Titelreaktion in THF liefert neben Halogenopentacarbonylmetallaten die Komplexe (I), die anha... more

ChemInform Abstract: Reaktionsweisen des Tricarbonyl‐eisen‐cycloheptatrienid‐Anions [C7H7Fe(CO)3] ‐

Chemischer Informationsdienst, 1976

ChemInform Abstract: REAKTIONEN VON K2(FE2(CO)8) MIT PH3SNCL UND PH2SNCL2

Chemischer Informationsdienst, 1978

Bei der Titelreaktion in THF bei Raumtemp. bleibt die Metall‐Metall‐Bindung des Diferrats erhalten.

Über neue Cyano-nitrosylmanganate und Isonitril-nitrosyl-Komplexe des Mangans/On New Cyano Nitrosyl Manganates and Isonitrile Nitrosyl Complexes of Manganese

Zeitschrift für Naturforschung B, 1983

The anionic cyano nitrosyl manganates [Mn(NO)(CO)3CN] - and [Mn(NO)3CN]- are formed by the reacti... more The anionic cyano nitrosyl manganates [Mn(NO)(CO)3CN] - and [Mn(NO)3CN]- are formed by the reactions of Mn(NO)(CO)4 and Mn(NO)3CO with NaN(SiMe3)2. The alkylation of these anions with [R3O]BF4 (R = Me, Et) leads to the corresponding isonitrile complexes Mn(NO)(CO)3CNR and Mn(NO)3CNR. IR, mass and 13C NMR spectra indicate trigonal-bipyramidal coordination for nitrosyl tricarbonyl derivatives, with three CO ligands in facial positions and NO in the equatorial plane. Based on the temperature dependent 13C NMR spectra of Mn(NO)(CO)3CNR and Mn(NO)(CO)4 the fluctional behaviour of these compounds could be demonstrated with ⊿G+ values of 48 kJ/mol or less for the CO exchange.

Darstellung und Eigenschaften neuer Dichloro‐bis(carbonylmetallato)‐zinn(IV)‐Verbindungen

Zeitschrift für anorganische und allgemeine Chemie, 1979

Bei der Umsetzung der Trichloro‐(carbonylmetallato)‐zinn(IV)‐Verbindungen Cl3SnMn(CO)4L (L = CO, ... more Bei der Umsetzung der Trichloro‐(carbonylmetallato)‐zinn(IV)‐Verbindungen Cl3SnMn(CO)4L (L = CO, PEt2Ph) und Cl3SnFe(CO)2Cp (Cp = η5‐C5H5) mit den Thallium(I)‐carrbonylmetallaten TlCo(CO)4 und TlCr(CO)3Cp im Molverhältnis 1:1 entstehen in gezielter Synthese die in Tab. 1 aufgeführten Bis(carbonylmetallato)‐zinn(IV)‐Komplexe, deren Massen‐, IR‐ und IR‐Spektren diskutiert werden.

Phosphinsubstituierte chelatliganden I. Mangan- und rheniumcarbonyl-komplexe mit phosphino-(thio)formamid- und -dithioformiat-liganden

Journal of Organometallic Chemistry, 1981

... Bibliographie. Bibliographie. 1. U. Kunze and A. Antoniadis. J. Organometal. Chem. 188 (1980)... more

Transition metal complexes with sulfur ligands. XXXI. Six and seven coordinate CO, NO, PMe3 and phosphineiminato molybdenum complexes with [Mo{S4}] frameworks ({S4}=2, 3; 8, 9-dibenzo-1,4, 7,10-tetrathiadecane( 2 -))

Inorganica Chimica Acta, 1988

Abstract In order to explain the high reactivity of [Mo- (NO)2(dttd)] towards phosphines the stru... more Abstract In order to explain the high reactivity of [Mo- (NO)2(dttd)] towards phosphines the structures of [Mo(CO)2(PMe3)(dttd)] and [Mo(NO)(NPMePh2)- (dttd)] have been determined by X-ray structure analysis and compared with the structures of other [M(dttd)] complexes (dttd2-=2,3;8,9-dibenzo- 1,4,7,10-tetrathiadecane(2-)). In [Mo(CO)2(PMe3)- (dttd)] the seven coordinate Mo center is ligated by one P, two C and four sulfur atoms. [Mo(NO)(NP- MePh2)(dttd)] contains a six coordinate molybenum atom pseudooctahedrally surrounded by two N and four S atoms and possesses a bent [MNP] entity with an exceedingly small angle of 129.7(4)°; the pseudooctahedral [MS4] core in [M(dttd)] fragments is flexible enough to accommodate the coordination of two as well as three further coligands. The reaction between [Mo(NO)2(dttd)] and phosphines PR3 yielding the phosphineiminato complexes [Mo(NO)- (NPR3)(dttd)] is dominated by the nucleophilicity of PR3 as is shown by the fast reactions with PMe3 and PCy3 and the slow reactions with arylphosphines. [MNP] angles and νas(MNP) frequencies in [M- (phosphineiminato)] complexes correlate: small angles compare with low frequencies. 13C, 95Mo and 14N NMR data of the complexes are discussed and indicate the oxidation of Mo and the reduction of the nitrogen of one NO ligand, when [Mo(NO)2- (dttd)] is converted into [Mo(NO)(NPR3)(dttd)]; NPR3 ligands act as strong 4e- donors.

Reaktionsweisen des Tricarbonyl-eisen-cycloheptatrienid-Anions [C7H7Fe(CO)3]

Zeitschrift für Naturforschung B, 1976

The reactions of [C7H7Fe(CO)3]- with alkyl chloroformates leads to the formation of ester substit... more The reactions of [C7H7Fe(CO)3]- with alkyl chloroformates leads to the formation of ester substituted cycloheptatriene iron tricarbonyls 7-R-C7H7Fe(CO)3 and 1-R-C7H7Fe(CO)3. In contrast, similar reactions with (C2H5ECl give only the 7-isomers (C2H3)3E-C7H7Fe(CO)3 (E = Si, Ge). The synthesis of the doubly ester-substituted cycloheptatriene iron tricarbonyl (C2H5OCO)2C7H6Fe(CO)3 is described.

Übergangsmetallkomplexe mit Schwefelliganden, LXXX. Synthese, Struktur, Oxotransfer- und redoxgekoppelte Kondensationsreaktionen von Molybdän-Oxo-Komplexen mit dem sterisch anspruchsvollen vierzähnigen Thioether-Thiolat-Liganden 'buS4'2- ('buS4'2- = 1,2-Bis(2-mercapto-3,5-di-t-butylphenylthio)eth...

Zeitschrift für Naturforschung B, 1992

In order to obtain soluble molybdenum sulfur oxo complexes, [Mo(O)2('buS4')] (1) ('bu... more In order to obtain soluble molybdenum sulfur oxo complexes, [Mo(O)2('buS4')] (1) ('buS4'2- = 1,2-bis(2-mercapto-3,5-di-t-butylphenylthio)ethane(2-)) was synthesized by reaction of [Mo(O)2(acac)2] (acac- = acetylacetonate(1-) ) with 'buS4'-Li2. Treatment of 1 with PPh3 yielded [μ-O{Mo(O)('buS4')}2] (2) and OPPh3 in an oxo transfer reaction. [Mo(PMe3)2('buS2')2] (3) ('buS2'2- = 3,5-di-t-butyl-1,2 -benzenedithiolate(2-)) was obtained by twofold desoxygenation of 1 with excess PMe3 via a redox coupled addition elimination reaction. 2 reacts with the oxo group donor DMSO to yield 1 and Me2S. The system 1/2 then catalyses the oxo transfer reaction from DMSO to PPh3 and, therefore, shows properties modelling the co-factor in oxotransferases. In contrast to the parent compound [Mo(O)2('S4')] ('S4'2- = 1,2-bis(2-mercaptophenylthio)ethane(2-)), 1 is reactive towards hydrazine and its derivatives. Reactions with hydrazine and alky...

Chemie polyfunktioneller liganden

Journal of Organometallic Chemistry, 1981

Übergangsmetallkomplexe mit Schwefelliganden, XCl+ Fell-Komplexe des fünfzähnigen Thioether-Thiolat-Aminliganden ′buNHS4′-H2: Synthese, Charakterisierung, Reaktivität und Stereochemie (′buNHS4′-H2 = 2,2′-Bis(2-mercapto-3,5-di-tertiärbutyl-phenylthio)diethylamin) / Transition Metal Complexes with ...

Zeitschrift für Naturforschung B, Aug 1, 1992

In search o f m odel com pounds for the active centers o f nitrogenases, [Fe(L)('buN HS4')] compl... more In search o f m odel com pounds for the active centers o f nitrogenases, [Fe(L)('buN HS4')] complexes o f the pentadentate thioether-thiolate-amine ligand 'buN HS4'2-('buN HS4'-H2 = 2,2'-bis(2-mercapto-3,5-di-tertiarybutyl-phenylthio)diethylamine) were obtained. A lkylation o f 'buS2'-H2 with (BrC2H4),N H yielded the new ligand 'buN HS4'-H2 as a mixture o f positional isomers. Isolation o f single isomers was achieved by reacting the mixture with FeCl2-4 H 20 and CO in order to give the corresponding [Fe(CO)] complexes which were se parated and hydrolyzed to yield the free ligands. R eaction o f 'buN HS4'-H2 with FeCl2 -4 H 20 led to the high-spin complex [Fe('buN HS4')] which is extremely air-sensitive in solution. It rapidly reacts with L = CO, NO, PM e3, and N 2H4, and is the m ost suitable starting material for syntheses o f [Fe(L)('buN HS4')l complexes which were characterized for L = CO, N O +, N O , PM e3 and N 2H4. All complexes are considerably better soluble in organic solvents than the corresponding parent compounds [Fe(L)('NHS4')], ('N hS4'-H 2 = 2,2'-bis(2-mercaptophenylthio)diethylamine), but have similar properties in most other respects. In the oxidation o f [F e(N 2H 4)('buN HS4')] at low temperatures, there is evidence for the form ation o f the diazene com plex [u-N 2H2{Fe('buN HS4')}2].

Übergangsmetallkomplexe mit Schwefelliganden, LVIII / Transition Metal Complexes with Sulfur Ligands, LVIII

Zeitschrift für Naturforschung B, Mar 1, 1991

In stitu t für A norganische Chem ie d er U niversität, E gerlandstraße 1, D-8520 E rlangen Z. N ... more In stitu t für A norganische Chem ie d er U niversität, E gerlandstraße 1, D-8520 E rlangen Z. N atu rfo rsch . 46b, 3 0 3 -3 0 6 (1991); eingegangen am 10. O k to b er 1990 R u thenium , C row n T hioethers, V inyl-Thioether, Sulfur Ligands T he m o no catio n [R u('S6'-C H = C H 2)]+, [2]+, ('S6'-C H = C H 2-= 2.3.11.12-dibenzo-1.4.7.10.13.16-hexathiaoctadec-17-ene(l -)) form s u n d er norm al co n d itio n s by S -C bond cleavage in an irreversible and selective reaction on treating salts o f the d ication [R u (b zo 2-18S6)]2+, [1]2+, (bzo-,-18S6 = 2 .3 .1 1.12-dibenzo-1.4.7.10.13.16-hexathiacyclooctadecane) with one equivalent o f base. T his reaction dem o n strates the drastic S -C activation in co o rd in ated thioethers and should be tak en into consideration w hen cofactors are isolated from m etal sul fur enzym es. * LVII. M itteilung s. Ref. [1], ** S ond erd ru ck an fo rd eru n g en an Prof. D r. D. Sell m ann.

Übergangsmetallkomplexe mit Schwefelliganden, LX / Transition Metal Complexes with Sulfur Ligands, LX

Zeitschrift für Naturforschung B, May 1, 1991

Transition M etal Complexes with Sulfur Ligands, LX* Synthesis, Properties and Reactivity of Isom... more Transition M etal Complexes with Sulfur Ligands, LX* Synthesis, Properties and Reactivity of Isomerically Pure [Fe(L)'buSs'] Complexes with L = CO, NO, N O +, P(OPh)3 ('buS5'2-= Dianion of 2,2'-Bis(2-mercapto-3,5-di-tertiary-butylphenylthio)diethylsulfide) Dieter Sellm ann+, Klaus Höhn und M atthias Moll In stitu t für A norganische C hem ie der U n iversität E rlan g e n -N ü rn b erg , E g erla n d straß e 1, D-8520 E rlangen Z. N atu rfo rsch . 46b, 6 6 5 -6 7 2 (1991); eingegangen am 19. N o v em b er 1990 Iron S ulfur C om plexes, Synthesis, R eactions, Stereochem istry, T ran sitio n M etal Com plexes T he p en tad e n tate th io eth er thiolate ligand 'buS5'2-(= d ian io n o f 2,2'-bis(2-m ercapto-3,5-di-tertiary-butylphenylthio)diethylsulfide) reacts w ith iro n (II) ions to give the diam agnetic [F e'buS5'] (1), which only co o rd in ates o ~n ligands such as C O , N O , N O + o r P (O P h )3. In this respect, the [F e'buS5'] fragm ent differs from the p aren t com plex [F e'S /] ('S 5'2~ = d ianion o f 2,2'-bis(2-m ercaptophenylthio)diethylsulfide) as well as from the related [F e'N HS4'] ('N HS4'2~ = dian io n o f 2,2'-bis(2-m ercaptophenylthio)diethylam ine), b o th o f which are able to co o rd in ate also rr-ligands such as N 2H 4 o r N H 3. Synthesis o f [F e(C O )'buS5'] (2), yields tw o stereoisom ers th a t can be easily separated ow ing to their different solubility.

Übergangsmetallkomplexe mit Schwefelliganden, LXXX. Synthese, Struktur, Oxotransfer- und redoxgekoppelte Kondensationsreaktionen von Molybdän-Oxo-Komplexen mit dem sterisch anspruchsvollen vierzähnigen Thioether-Thiolat-Liganden '<sup>bu</sup>S<sub>4</sub>'<sup>2-</sup> ('<sup>bu</sup>S<sub>4</su...

Zeitschrift für Naturforschung B, 1992

Transition Metal Complexes with Sulfur Ligands, LXXX* Syntheses, Structures, Oxo Transfer and Red... more Transition Metal Complexes with Sulfur Ligands, LXXX* Syntheses, Structures, Oxo Transfer and Redox Coupled Condensation Reactions o f M olybdenum Oxo Complexes with the Sterically Demanding Tetradentate Thioether-Thiolato-Ligand 'buS4'2-('bug^'2-_ i,2-Bis(2-m ercapto-3,5-di-/-butylphenylthio)ethane(2-))

Notizen: Protonierung und Alkylierung von Olefin-cyano-dicarbonyl-ferraten(0)

Zeitschrift für Naturforschung B, Aug 1, 1976

Olefin Dicarbonyl Iron(O) Isocyanic Acids, Olefin Isonitrile Dicarbonyl Iron The anionic complexe... more Olefin Dicarbonyl Iron(O) Isocyanic Acids, Olefin Isonitrile Dicarbonyl Iron The anionic complexes [olenFe(CO)2CN]~ (olen = butadiene, 1,3-cyclohexadiene, cyclooctatetraene), formed by the reaction of olenFe(CO)3 with NaN[Si(CH3)3]2, have been protonated to the isocyanic acid derivates olenFe(CO)2CNH, and alkylated with [Et30]BF4 to give the isonitrile complexes olenFe(CO)2CNEt.

Übergangsmetallkomplexe mit Schwefelliganden, XXIV* Reduktive Nitrosylierung von [MoCl2(dttd)] zu [Mo(NO)2(dttd)];Eigenschaften, Struktur und Reaktion zu NPR3-Komplexen[Mo(NO)(NPR3)dttd] (PR3=PMe3, PEt3, PMePh2, PEtPh2, PPh3;dttd2-=2,3,8,9-Dibenzo-1,4,7,10-tetrahiadecan(2-)) / Transition Metal Co...

Zeitschrift für Naturforschung B, 1986

In order to study the properties of sulfur coordinated transition metal centers. [MoCl2dttd] (dtt... more In order to study the properties of sulfur coordinated transition metal centers. [MoCl2dttd] (dttd2 = 2,3,8,9-dibenzo-1,4.7,10-tetrathiadecane(2-)) was reacted with NO in the presence of Zn. [Mo(NO)2dttd] was obtained whose X-ray structure analysis shows that Mo is coordinated pseudo-octahedrally by two trans thiolato S, two cis thioether S as well as two cis N atoms of nearly linear MoNO groups. With respect to its low v(NO) frequencies (1760/1665 cm -1) and quite normal bond lengths as well as angles [Mo(NO)2dttd] shows unexpectedly facile and rapid reactions with nucleophiles; with two equivalents of PR3 (PMe3, PEt3, PMePh2, PEtPh2, PPh3) it yields the corresponding phosphiniminato complexes [Mo(NO)(NPR3)dttd] and free phosphinoxides OPR3, respectively. Reaction mechanisms as well as the bonding situation in the [Mo(NPR3)] entity are discussed; on the basis of 95Mo and 14N NMR it is concluded that the conversion of NO into NPR3 ligands includes a reduction of N(+2) to N(-3) as we...

Übergangsmetallkomplexe mit Schwefelliganden, LXX. / Transition Metal Complexes with Sulfur Ligands, LXX

Zeitschrift für Naturforschung B, Nov 1, 1991

'S4')] IM o(i^-NH20)(N O)('S 4')]-Reduktion ('S4'2-= l,2-Bis(2-mercaptophenylthio)ethan(2-)) Tran... more

Transition-metal complexes with sulfur ligands. 45. Model reactions for oxidoreductases with metal-sulfur centers: proton-induced triphenylphosphine/hydrochloric acid exchange in [Ru(PPh3)2(L)] and properties of the resulting HCl complexes [Ru(ClH)(PPh3)(L)] (L = 1,2-bis((2-mercaptophenyl)thio)et...

Inorganic Chemistry, 1990

We discuss the influence of thiolate ligands at metal-sulfur centers, in particular with respect ... more We discuss the influence of thiolate ligands at metal-sulfur centers, in particular with respect to reactions involving protons. Aims of these investigations were the identification of the reaction products of [Ru(PPh 3 ) 2 (L)] (L= bu S 4 2- , S 4 2- ) with HCl, better insight into the reaction mechanisms, syntheses of new complexes with the [Ru(L)] fragments, and elucidation of potential bioinorganic relevances

ChemInform Abstract: Transition Metal Complexes with Sulfur Ligands. Part 31. Six‐ and Seven‐Coordinate CO, NO, PMe3 and Phosphineiminato Molybdenum Complexes with (Mo(S4)) Frameworks ((S4) = 2,3;8,9‐dibenzo‐1,4,7,10‐tetrathiadecane(2‐))

ChemInform, 1988

In order to explain the high reactivity of the Mo complex (III) towards tert. phosphines the stru... more In order to explain the high reactivity of the Mo complex (III) towards tert. phosphines the structures of the seven‐coordinate trimethylphosphinedicarbonyl complex (I) and the six‐coordinate phosphine imidato complex (II) (for both space group P21/c, Z=4) are determined by X‐ray analysis and compared to structures of analogous complexes.

ChemInform Abstract: Transition Metal Complexes with Sulfur Ligands. Part 28. Ruthenium Complexes of the Pentadentate Thioether Thiolate Ligands dpttd2‐ (2,3,11,12‐Dibenzo‐1,4,7,10,13‐pentathiatridecane(‐2)) and the Sterically Demanding Derivative tBu4‐dpttd2‐ (14,16,18,20‐Tetra(t‐butyl)‐2,3,11,1...

ChemInform, 1987

According to the scheme, the template alkylation of 1,2‐benzenedithiolate by bis(β‐bromoethyl) su... more

ChemInform Abstract: REAKTIONEN VON NA2(M2(CO)10) (M=CR,MO,W) MIT INX3 (X=CL,BR,I) UND DIE KRISTALLSTRUKTUR VON CR(CO)5INBR.THF

Chemischer Informationsdienst, 1978

Die Titelreaktion in THF liefert neben Halogenopentacarbonylmetallaten die Komplexe (I), die anha... more

ChemInform Abstract: Reaktionsweisen des Tricarbonyl‐eisen‐cycloheptatrienid‐Anions [C7H7Fe(CO)3] ‐

Chemischer Informationsdienst, 1976

ChemInform Abstract: REAKTIONEN VON K2(FE2(CO)8) MIT PH3SNCL UND PH2SNCL2

Chemischer Informationsdienst, 1978

Bei der Titelreaktion in THF bei Raumtemp. bleibt die Metall‐Metall‐Bindung des Diferrats erhalten.

Über neue Cyano-nitrosylmanganate und Isonitril-nitrosyl-Komplexe des Mangans/On New Cyano Nitrosyl Manganates and Isonitrile Nitrosyl Complexes of Manganese

Zeitschrift für Naturforschung B, 1983

The anionic cyano nitrosyl manganates [Mn(NO)(CO)3CN] - and [Mn(NO)3CN]- are formed by the reacti... more The anionic cyano nitrosyl manganates [Mn(NO)(CO)3CN] - and [Mn(NO)3CN]- are formed by the reactions of Mn(NO)(CO)4 and Mn(NO)3CO with NaN(SiMe3)2. The alkylation of these anions with [R3O]BF4 (R = Me, Et) leads to the corresponding isonitrile complexes Mn(NO)(CO)3CNR and Mn(NO)3CNR. IR, mass and 13C NMR spectra indicate trigonal-bipyramidal coordination for nitrosyl tricarbonyl derivatives, with three CO ligands in facial positions and NO in the equatorial plane. Based on the temperature dependent 13C NMR spectra of Mn(NO)(CO)3CNR and Mn(NO)(CO)4 the fluctional behaviour of these compounds could be demonstrated with ⊿G+ values of 48 kJ/mol or less for the CO exchange.

Darstellung und Eigenschaften neuer Dichloro‐bis(carbonylmetallato)‐zinn(IV)‐Verbindungen

Zeitschrift für anorganische und allgemeine Chemie, 1979

Bei der Umsetzung der Trichloro‐(carbonylmetallato)‐zinn(IV)‐Verbindungen Cl3SnMn(CO)4L (L = CO, ... more Bei der Umsetzung der Trichloro‐(carbonylmetallato)‐zinn(IV)‐Verbindungen Cl3SnMn(CO)4L (L = CO, PEt2Ph) und Cl3SnFe(CO)2Cp (Cp = η5‐C5H5) mit den Thallium(I)‐carrbonylmetallaten TlCo(CO)4 und TlCr(CO)3Cp im Molverhältnis 1:1 entstehen in gezielter Synthese die in Tab. 1 aufgeführten Bis(carbonylmetallato)‐zinn(IV)‐Komplexe, deren Massen‐, IR‐ und IR‐Spektren diskutiert werden.

Phosphinsubstituierte chelatliganden I. Mangan- und rheniumcarbonyl-komplexe mit phosphino-(thio)formamid- und -dithioformiat-liganden

Journal of Organometallic Chemistry, 1981

... Bibliographie. Bibliographie. 1. U. Kunze and A. Antoniadis. J. Organometal. Chem. 188 (1980)... more

Transition metal complexes with sulfur ligands. XXXI. Six and seven coordinate CO, NO, PMe3 and phosphineiminato molybdenum complexes with [Mo{S4}] frameworks ({S4}=2, 3; 8, 9-dibenzo-1,4, 7,10-tetrathiadecane( 2 -))

Inorganica Chimica Acta, 1988

Abstract In order to explain the high reactivity of [Mo- (NO)2(dttd)] towards phosphines the stru... more Abstract In order to explain the high reactivity of [Mo- (NO)2(dttd)] towards phosphines the structures of [Mo(CO)2(PMe3)(dttd)] and [Mo(NO)(NPMePh2)- (dttd)] have been determined by X-ray structure analysis and compared with the structures of other [M(dttd)] complexes (dttd2-=2,3;8,9-dibenzo- 1,4,7,10-tetrathiadecane(2-)). In [Mo(CO)2(PMe3)- (dttd)] the seven coordinate Mo center is ligated by one P, two C and four sulfur atoms. [Mo(NO)(NP- MePh2)(dttd)] contains a six coordinate molybenum atom pseudooctahedrally surrounded by two N and four S atoms and possesses a bent [MNP] entity with an exceedingly small angle of 129.7(4)°; the pseudooctahedral [MS4] core in [M(dttd)] fragments is flexible enough to accommodate the coordination of two as well as three further coligands. The reaction between [Mo(NO)2(dttd)] and phosphines PR3 yielding the phosphineiminato complexes [Mo(NO)- (NPR3)(dttd)] is dominated by the nucleophilicity of PR3 as is shown by the fast reactions with PMe3 and PCy3 and the slow reactions with arylphosphines. [MNP] angles and νas(MNP) frequencies in [M- (phosphineiminato)] complexes correlate: small angles compare with low frequencies. 13C, 95Mo and 14N NMR data of the complexes are discussed and indicate the oxidation of Mo and the reduction of the nitrogen of one NO ligand, when [Mo(NO)2- (dttd)] is converted into [Mo(NO)(NPR3)(dttd)]; NPR3 ligands act as strong 4e- donors.

Reaktionsweisen des Tricarbonyl-eisen-cycloheptatrienid-Anions [C7H7Fe(CO)3]

Zeitschrift für Naturforschung B, 1976

The reactions of [C7H7Fe(CO)3]- with alkyl chloroformates leads to the formation of ester substit... more The reactions of [C7H7Fe(CO)3]- with alkyl chloroformates leads to the formation of ester substituted cycloheptatriene iron tricarbonyls 7-R-C7H7Fe(CO)3 and 1-R-C7H7Fe(CO)3. In contrast, similar reactions with (C2H5ECl give only the 7-isomers (C2H3)3E-C7H7Fe(CO)3 (E = Si, Ge). The synthesis of the doubly ester-substituted cycloheptatriene iron tricarbonyl (C2H5OCO)2C7H6Fe(CO)3 is described.

Übergangsmetallkomplexe mit Schwefelliganden, LXXX. Synthese, Struktur, Oxotransfer- und redoxgekoppelte Kondensationsreaktionen von Molybdän-Oxo-Komplexen mit dem sterisch anspruchsvollen vierzähnigen Thioether-Thiolat-Liganden 'buS4'2- ('buS4'2- = 1,2-Bis(2-mercapto-3,5-di-t-butylphenylthio)eth...

Zeitschrift für Naturforschung B, 1992

In order to obtain soluble molybdenum sulfur oxo complexes, [Mo(O)2('buS4')] (1) ('bu... more In order to obtain soluble molybdenum sulfur oxo complexes, [Mo(O)2('buS4')] (1) ('buS4'2- = 1,2-bis(2-mercapto-3,5-di-t-butylphenylthio)ethane(2-)) was synthesized by reaction of [Mo(O)2(acac)2] (acac- = acetylacetonate(1-) ) with 'buS4'-Li2. Treatment of 1 with PPh3 yielded [μ-O{Mo(O)('buS4')}2] (2) and OPPh3 in an oxo transfer reaction. [Mo(PMe3)2('buS2')2] (3) ('buS2'2- = 3,5-di-t-butyl-1,2 -benzenedithiolate(2-)) was obtained by twofold desoxygenation of 1 with excess PMe3 via a redox coupled addition elimination reaction. 2 reacts with the oxo group donor DMSO to yield 1 and Me2S. The system 1/2 then catalyses the oxo transfer reaction from DMSO to PPh3 and, therefore, shows properties modelling the co-factor in oxotransferases. In contrast to the parent compound [Mo(O)2('S4')] ('S4'2- = 1,2-bis(2-mercaptophenylthio)ethane(2-)), 1 is reactive towards hydrazine and its derivatives. Reactions with hydrazine and alky...

Chemie polyfunktioneller liganden

Journal of Organometallic Chemistry, 1981