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

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.

1991 ◽  
Vol 46 (12) ◽  
pp. 1585-1592 ◽  
Author(s):  
Dieter Sellmann ◽  
Peter Lechner ◽  
Falk Knoch ◽  
Matthias Moll

Under exclusion of air the thioether and thiol complexes [Ru(SRR′)(PPh3)′S4′] (′S4′2- = 1,2-bis(2-mercaptophenylthio)ethane (2—)) easily react with CHCl3 yielding [Ru(Cl)(PPh3)(′S4′—CHCl2)] in which one thiolato atom of the ′S4′ ligand is diastereospecifically dichloromethylated. In the presence of air, however, [RuIII(Cl)(PPh3)′S4′] is formed.The molecular structures of [Ru(Cl)(PPh3)(′S4′-CHCl2)] · 2CHCl3 and [RuIII(Cl)(PPh3)′buS4′] have been determined by X-ray crystallography. ′buS4′2- (= 1,2-bis(3,5-di(t-butyl)-2-mercaptophenylthio)ethane(2-)) is the t-butyl derivative of the ′S4′ ligand. Reasons for observed diastereospecifity of alkylation are discussed.


2008 ◽  
Vol 47 (17) ◽  
pp. 7468-7470 ◽  
Author(s):  
Tyler J. Morin ◽  
Brian Bennett ◽  
Sergey V. Lindeman ◽  
James R. Gardinier

1983 ◽  
Vol 38 (5) ◽  
pp. 562-567 ◽  
Author(s):  
Bharat B. Kaul ◽  
D. Sellmann

AbstractSynthesis and characterization of non-oxo Mo(IV) complexes with the tetradentate thioether-thiol ligand 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane(dttd-H2) are reported. MoCl4(THF)2 reacts with dttd-H2 in THF at room temperature to give the paramagnetic (2.61 BM, 295 K) [Mo(dttd)Cl2]. The chlorine ligands in [Mo(dttd)Cl2] can be substituted by sulfur ligands yielding diamagnetic complexes as [Mo(dttd)(CeH4S2)], [Mo(dttd)(SC2H4S)] and [Mo(dttd)(SC2H5)2]; with Na2S, NaHS or H2S, the di-μ-sulfido bridged complex [(dttd)Mo(S)2Mo(dttd)] is obtained. The reduction of [Mo(dttd)Cl2] by various reducing agents in the presence of CO or NO yields labile carbonyl and nitrosyl species in solution. In contrast to [Mo(dttd)Cl2], the complexes with MoSe cbromophores showed no reactivity to CO or NO under reducing conditions.


1995 ◽  
Vol 50 (8) ◽  
pp. 1229-1244 ◽  
Author(s):  
Dieter Sellmann ◽  
Christine Rohm ◽  
Matthias Moll ◽  
Falk Knoch

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.


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