Synthesis and Structures of s- and p-Block Metal Complexes Containing Sterically Demanding Pentaarylcyclopentadienyl Substituents

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-).

Download Full-text

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

European Journal of Inorganic Chemistry ◽

10.1002/ejic.200900170 ◽

2009 ◽

Vol 2009 (17) ◽

pp. 2547-2552 ◽

Cited By ~ 17

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

Download Full-text

Lanthanoiden-Komplexe, IX [1]. Reaktivitätsbestimmender Einfluß der Ligandenkonstitution bei Seltenerdamiden: Herstellung und Struktur sterisch überladener Alkoxid-Komplexe / Lanthanoid Complexes, IX [1]. Reactivity Control of Lanthanoid Amides through Ligand Effects: Synthesis and Structures of Sterically Congested Alkoxy Complexes

Zeitschrift für Naturforschung B ◽

10.1515/znb-1994-1225 ◽

1994 ◽

Vol 49 (12) ◽

pp. 1789-1797 ◽

Cited By ~ 87

Author(s):

Wolfgang A. Herrmann ◽

Reiner Anwander ◽

Florian C. Munck ◽

Wolfgang Scherer ◽

Veronique Dufaud ◽

...

Keyword(s):

Metal Complexes ◽

Crystal Structures ◽

Ligand Effects ◽

Sterically Demanding ◽

Molecular And Crystal Structures ◽

Homoleptic Complexes

It is shown that the introduction of sterically demanding ligands in lanthanoid metal complexes can depend more on the precise composition of the lanthanoid precursor than on the size of the new ligand. Thus, tris(r-butyl)methanol (“rmojt-H”) does not react with the amides Ln[N(SiMe3)2]3 of the “late” (small) lanthanoid metals. However, fast and clean reactions occur with the sterically less demanding derivatives Ln[N(SiHMe2)2]3, with new homoleptic complexes Ln(tritox)3 (Ln = Y, Nd) being formed with practically all metals of this group of elements. The molecular and crystal structures of some lanthanoid amides and alkoxides are described.

Download Full-text

Transition metal complexes with sterically demanding ligands. I. Synthesis and X-ray crystal structure of 1,5-cyclooctadiene palladium methyl triflate, (COD)Pd(Me)(OTf) and its cationic penta-coordinate adducts with sterically demanding 2,9-diaryl-substituted 1,10-phenanthroline ligands

Journal of Organometallic Chemistry ◽

10.1016/s0022-328x(98)00997-8 ◽

1999 ◽

Vol 575 (2) ◽

pp. 214-222 ◽

Cited By ~ 25

Author(s):

Peter Burger ◽

JanM Baumeister

Keyword(s):

Crystal Structure ◽

Transition Metal ◽

Metal Complexes ◽

Transition Metal Complexes ◽

X Ray ◽

Sterically Demanding ◽

Phenanthroline Ligands ◽

Methyl Triflate

Download Full-text

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-dp

ChemInform ◽

10.1002/chin.198744301 ◽

1987 ◽

Vol 18 (44) ◽

Author(s):

D. SELLMANN ◽

G. BINKER ◽

M. MOLL ◽

C. E. CAMPANA

Keyword(s):

Transition Metal ◽

Metal Complexes ◽

Transition Metal Complexes ◽

Ruthenium Complexes ◽

Thiolate Ligands ◽

Sterically Demanding

Download Full-text

Kinetic stabilization of low-oxidation state and terminal hydrido main group metal complexes by a sterically demanding N,N′-bis(2,6-terphenyl)triazenide

Dalton Transactions ◽

10.1039/c9dt02562f ◽

2019 ◽

Vol 48 (35) ◽

pp. 13197-13204 ◽

Cited By ~ 7

Author(s):

Anthony R. Leverett ◽

Vera Diachenko ◽

Marcus L. Cole ◽

Alasdair I. McKay

Keyword(s):

Metal Complexes ◽

Oxidation State ◽

Main Group ◽

Group Metal ◽

Main Group Metal ◽

Sterically Demanding ◽

Low Oxidation State ◽

Hydride Ligands

Thermally robust main group metal complexes featuring terminal hydride ligands are achieved by deploying a sterically demanding N,N′-bis(2,6-terphenyl)triazenide ligand.

Download Full-text

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)

Zeitschrift für Naturforschung B ◽

10.1515/znb-1995-0818 ◽

1995 ◽

Vol 50 (8) ◽

pp. 1229-1244 ◽

Cited By ~ 6

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.

Download Full-text