ChemInform Abstract: Transition-Metal Complexes with Sulfur Ligands. Part 44. Ruthenium(II) Complexes with the Sterically Demanding Thioether-Thiolate Ligand “buS4”2-(= 1,2-Bis(3,5-di(tertiarybutyl)-2-mercaptophenylthio)ethane (2-)) and PPh3, CO, PMe3, NH

ChemInform ◽  
1990 ◽  
Vol 21 (12) ◽  
Author(s):  
D. SELLMANN ◽  
I. BARTH
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Thiolate Ligand ◽  
Sterically Demanding

Ubergangsmetallkomplexe mit Schwefelliganden, CIX. Synthese und Reaktivität von meso-[Ru(L)('buS5')]-Komplexen mit L = NO+, CO, PR3 (R = Me, Ph, Cy), pyr, CN-, N2H4, NH2NHR (R = Me, Ph), NH2NMe2, NH3, NH2Ph, NHEt2 ('buS5' - H2 = 2,2'-Bis(2-mercapto-3,5-di-t-butylphenylthio)di-ethylsulfid) / Transition Metal Complexes with Sulfur Ligands, CIX. Synthesis and Reactivity of meso-[Ru(L)('buS5')] Complexes with L = NO+, CO, PR3 (R = Me, Ph, Cy), pyr, CN-, N2H4, NH2NHR (R = Me, Ph), NH2NMe2, NH3, NH2Ph, NHEt2 ( 'buS5' - H2 = 2,2'-Bis(2-mercapto-3,5-di-t-butylphenylthio)diethylsulfide)

1995 ◽  
Vol 50 (8) ◽  
pp. 1229-1244 ◽  
Author(s):  
Dieter Sellmann ◽  
Christine Rohm ◽  
Matthias Moll ◽  
Falk Knoch
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Mirror Plane ◽  
Fold Axis ◽  
Coordination Sites ◽  
Thiolate Ligand ◽  
Sterically Demanding ◽  
Coordination Spheres ◽  
Butyl Benzene

In a search of transition metal complexes with sulfur dominated coordination spheres and free coordination sites for the binding of small molecules, [Ru(L)('buS5')] complexes with the sterically demanding pentadentate thioether-thiolate ligand 'buS5'2- ( 'buS5'2- = 2,2'-Bis(2-mercapto-3,5-di-t-butylphenylthio)diethylsulfide(2-)) have been synthesized. Reaction of [RuCl3(NO)(PPh3)2] with 3,5-di(t-butyl)benzene-1,2-dithiolate, ′buS2'2-, yields the 16 electron complex [Ru(NO )('buS2')2]- which is isolated as the NBu4+-salt, 1. According to the NMR spectra, 1 contains a two-fold axis or a mirror plane. Alkylation of 1 with bis(β-bromethyl)sulfide under reflux leads stereoselectively to meso-[Ru(NO)('buS5')]Br, [2]Br. Reaction of [2]Br with LiBEt3H yields the barely soluble binuclear complex [Ru('buS5')]2, 3, with [Ru('buS5')Ru(NO)('buS2')('buS2'- C2H4SH)], 4, as a by-product. 4 ·THF, 4a, has been characterized by X-ray structure analysis. Reactions of 3 with σ-π- and σ-ligands yield mononuclear meso-[Ru(L)('buS5')] complexes which have been isolated and characterized with L = CO, PMe3, PPh3, PCy3, pyr, CN-, 5 - 10, NH2NHPh, NH2NHMe, NH2NMe2, NH2Ph und NHEt2, 13-17. Complexes 5 -10 are stable compounds. Complexes 13-17, however, are sensitive towards oxidation and/or substitution. Coordination of L = N2H4 and NH3 to 3 leads to insoluble [Ru(L)('buS5')]x complexes.

Übergangsmetallkomplexe mit Schwefelliganden, XXXII*: Synthese der sterisch anspruchsvollen Thiolat-amin-Liganden tbu2-ma-H = 2-Mercapto-3,5-di-tbutylanilin und tbu4-bmae-H2 = 1,2-Bis(2-mercapto-3,5-di-tbutylaniIino)ethan sowie ihrer Eisen-, Ruthenium- und Zink-Komplexe [Fe(CO)2(tbu2-ma)2], [Zn(tbu2-ma)2] und [RuL2(tbu4-bmae)], L = CO, PMe3, PPh3/ Transition Metal Complexes with Sulfur Ligands, XXXII*: Synthesis of the Sterically Demanding New Thiolate-amine Ligands tbu2-ma-H = 2-Mercapto-3,5-di-tbutylanilin und tbu4-bmae-H2 = 1,2-Bis(2-mercapto-3,5-di-tbutylaniIino)ethane as well as of their Iron-, Ruthenium- and Zinc Complexes [Fe(CO)2(tbu2-ma)2], [Zn(tbu2-ma)2] and [RuL2(tbu4-bmae)], L = CO, PMe3, PPh3

1987 ◽  
Vol 42 (10) ◽  
pp. 1291-1297 ◽  
Author(s):  
Dieter Sellmann ◽  
Olaf Käppler
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Acid Hydrolysis ◽  
Organic Solvents ◽  
Transition Metal Complexes ◽  
Zinc Complexes ◽  
Metal Centers ◽  
Sterically Demanding ◽  
Amine Ligands ◽  
Soluble Complexes

Abstract In order to obtain soluble complexes containing sterically protected metal centers the new bi- and tetradentate thiolate amine ligands 2-mercapto-3,5-di-tbutylaniline (= tbu2-ma-H) and 1,2-bis(2-mercapto-3,5-di-tbutylanilino)ethane (= tbu4-mae-H2) were synthesized. tbu2-ma-H reacts with FeCl2-4 H2O and CO to give [Fe(CO)2(tbu2-ma)2], with Zn(ac)2 -2 H2O [Zn(tbu2-ma)2] is obtained whose acid hydrolysis and reaction with H2S, respectively, yield pure tbu2-Ina-H. The condensation of tbu2-ma-H with glyoxal yields the respective bis-benzthiazolidine, which is re­duced by LiAlH4 in the presence of Na[N(SiMe3)2] to tbu4-bmae-H2. tbu4-bmae-Li2. reacts with [Ru(CO)3(THF)Cl2], [Ru(PMe3)4Cl2] and [Ru(PPh3)2(CH3CN)2Cl2], respectively, to yield [Ru(L)2(Tm4-bmae)j (L = CO, PMe3, PPh3). The complexes are more soluble in organic solvents than the corresponding unsubstituted bmae complexes, bmae2- = 1,2-bis(2-mercaptoanilino)- ethane(2-).

Synthesis and Characterisation of Low-Coordinate Transition-Metal Complexes Stabilised by Sterically Demanding Carbazolido Ligands

2009 ◽  
Vol 2009 (17) ◽  
pp. 2547-2552 ◽  
Author(s):  
Andrew E. Ashley ◽  
Andrew R. Cowley ◽  
Jennifer C. Green ◽  
David R. Johnston ◽  
David J. Watkin ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Sterically Demanding

Übergangsmetallkomplexe mit Schwefelliganden, XI* Molybdän-Oxo-Komplexe des Typs [Mo(IV)(O)(S2)2], [Mo(VI)(O)2(S4)], [MO(IV)(O)(S4)] und [Mo(IV)(O)(S5)] mit zwei-, vier- und fünfzähnigen Thioether-thiolat-Liganden (Sx = mehrzähniger Thioether-thiolat-Ligand) / Transition Metal Complexes with Sulfur Ligands, XI* Molybdenum Oxo Complexes of the Type [Mo(IV)(O)(S2)2], [Mo(VI)(O)2(S4)], [MO(IV)(O)(S4)] and [Mo(IV)(O) (S5)] with Bi-, Tetra- and Pentadentate Thioether-Thiolate Ligands (SX = Multidentate Thioether-Thiolate Ligand

1985 ◽  
Vol 40 (3) ◽  
pp. 368-372 ◽  
Author(s):  
Dieter Sellmann ◽  
Lothar Zapf
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Analogous Reaction ◽  
Thiolate Ligands ◽  
Oxo Complexes ◽  
Reductive Nitrosylation ◽  
Thiolate Ligand ◽  
Thiol Ligand ◽  
Pentadentate Ligand

MoClReacting [Mo(O)2(acac)2] (acac- = acetylacetonate) with the tetradentate thioether-thiol ligand 2,3,8.9-dibenzo-1,4,7,10-tetrathiadecane (dttd-H2) yields cis-[Mo(O)2(dttd)] ; this compound is reduced by PPh3 to give [MoO(dttd)], which is also obtained from [MoCl2(dttd)] and H2O. Depending upon the concentrations of the reactants [4(THF)2], CH3SC6H4SH and H2O , in THF the products [MoO(CH3SC6H4S)2] or [MoCl2(CH3SC6H4S)2] are formed. In the analogous reaction between [MoCl4(THF)2] and the pentadentate ligand 2,3,11,12-dibenzo- 1,4,7,10,13-pentathiatridecane (dpttd-H2) in THF/H2O. [MoO(dpttd)] is obtained exclusively. Due to their poor solubility, the Mo(IV)-oxo complexes show only limited reactivity only; with NO reductive nitrosylation to cis-Mo(NO)2 complexes is observed.

3d Early Transition Metal Complexes Supported by a New Sterically Demanding Aryloxide Ligand

2013 ◽  
Vol 52 (19) ◽  
pp. 11126-11135 ◽  
Author(s):  
Keith Searles ◽  
Ba L. Tran ◽  
Maren Pink ◽  
Chun-Hsing Chen ◽  
Daniel J. Mindiola
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Early Transition Metal ◽  
Sterically Demanding ◽  
Early Transition

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

1991 ◽  
Vol 46 (5) ◽  
pp. 665-672 ◽  
Author(s):  
Dieter Sellmann ◽  
Klaus Höhn ◽  
Matthias Moll
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Thiolate Ligand ◽  
Parent Complex

The pentadentate thioether thiolate ligand ′buS5′2 (= dianion of 2,2′-bis(2-mercapto-3,5-di-tertiary-butylphenylthio)diethylsulfide) reacts with iron(II) ions to give the diamagnetic [Fe′buS5′] (1), which only coordinates σ-π ligands such as CO, NO, NO+ or P(OPh)3. In this respect, the [Fe′buS5′] fragment differs from the parent complex [Fe′S5′] (′S5′2- = dianion of 2,2′-bis(2-mercaptophenylthio)diethylsulfide) as well as from the related [Fe′NHS4′] (′NHS4′2- = dianion of 2,2′-bis(2-mercaptophenylthio)diethylamine), both of which are able to coordinate also σ-ligands such as N,H4 or NH3. Synthesis of [Fe(CO)′buS5′] (2), yields two stereoisomers that can be easily separated owing to their different solubility.

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