Aminoethyl-Functionalized Cyclopentadienyl Complexes of d-Block Elements

Jutzi, Peter; Redeker, Thomas

doi:10.1002/(sici)1099-0682(199806)1998:6<663::aid-ejic663>3.3.co;2-p

Cited by 63 publications

(112 citation statements)

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“…[8] Another concept, which has been extremely successful, in particular in cyclopentadienyl chemistry, is ligand functionalization, whereby an additional coordinating site is linked to the periphery of the five-membered ring via a suitable bridging moiety. This prospering area has produced a large number of novel cyclopentadienyl ligands bearing pendant N-, [9,10] O-, [11] P-, As-, and S-donor groups. [12] If properly designed, these ligands can coordinate to a transition metal center in a chelating η 5 :η 1 -fashion, and several of these complexes have played a key role in homogeneous catalysis as so-called constraint-geometry catalyst systems.…”

Section: Introductionmentioning

confidence: 95%

Chelate Complexes of Functionalized Cycloheptatrienyl Ligands: 17- and 18-Electron Molybdenum Complexes with Linked Cycloheptatrienyl−Phosphane Ligands and Their Use in Transition Metal Catalysis

Tamm

Baum

Lügger

et al. 2002

Eur. J. Inorg. Chem.

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The synthesis of P-functionalized molybdenum chelate complexes incorporating the linked cycloheptatrienyl− phosphane ligand [2-(diphenylphosphanyl)phenyl]cycloheptatrienyl, o-Ph 2 P−C 6 H 4 −C 7 H 6 , is described. The air-stable ligand precursor [2-(cyclohepta-2,4,6-trienyl)phenyl]diphenylphosphane (2) can be obtained in large quantities by addition of lithiated 2-BrC 6 H 4 PPh 2 (1) to the tropylium cation C 7 H 7 + . Hydride abstraction employing the trityl cation, Ph 3 C + , results in the formation of the tricyclic phosphonium salt 3. The P-functionalized cycloheptatriene 2 acts as an eight-electron ligand on reaction with Mo(CO) 6 to afford the cycloheptatriene−phosphane complex [(o-Ph 2 PC 6 H 4 -η 6 -C 7 H 7 )Mo(CO) 2 (P−Mo)] (4) as a single, chiral regioisomer, which undergoes clean hydride abstraction on treatment

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Section: Introductionmentioning

confidence: 95%

Chelate Complexes of Functionalized Cycloheptatrienyl Ligands: 17- and 18-Electron Molybdenum Complexes with Linked Cycloheptatrienyl−Phosphane Ligands and Their Use in Transition Metal Catalysis

Tamm

Baum

Lügger

et al. 2002

Eur. J. Inorg. Chem.

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“…38 The molecular structures of 27•THF, 28•THF (Fig. 6), [28] 2 (Fig. 7), and 29 were established by X ray diffraction.…”

Section: (2 Phosphinoethyl)cyclopentadienyl Complexesmentioning

confidence: 99%

“…result of the activation of the heterocycle due to the coor dination of Me3 SiCl to the nitrogen atom followed by the nucleophilic addition of the cyclopentadienide anion at position 4 of pyridine.A successful result was achieved in the reaction of Na 39 with Me 3 SiCl in Pr2 i O at 100 °C, which made it pos sible to completely prevent the formation of by products and substantially decrease the time of the heterogeneous reaction compared to Li 39. It should be noted that the fraction of symmetric isomer 43a in the mixture was substantially higher than that in the case of starting cyclo pentadiene 39 (43a : (43b + 43c) ~ 1 : 1).The reactions of silylated cyclopentadienes 42 and 43 with ZrCl 4 afford monocyclopentadienyl derivatives 46 (see Ref.…”

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confidence: 99%

Zirconium and titanium complexes with side-chain functionalized cyclopentadienyl ligands

Krut’ko

2009

Russ Chem Bull

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The present review summarizes the results of studies of Zr and Ti complexes based on chelating side chain functionalized cyclopentadienyl ligands, which were synthesized by the author of the present review and co workers. The coordination ability of the functional groups is considered. Dynamic processes that occur in half sandwich complexes in solutions were studied by NMR spectroscopy. Emphasis is given to the reduction reactions of side chain functionalized zirconocene dichlorides, as well as to the structures and properties of the reaction products depending on the nature of the heteroatomic substituent.The present review summarizes data on Zr and Ti complexes with chelating cyclopentadienyl ligands con taining a functional (heteroorganic) group C 5 R 4 CH 2 CH 2 X (R = H and X = PMe 2 , PPh 2 , P(O)Ph 2 , or P(S)Ph 2 ; R = Me and X = OMe, SMe, NMe 2 , PMe 2 , or PPh 2 ) or C 5 Me 4 CH 2 (2 Py) in the side chain. The types of sand wich and half sandwich complexes I-IV that were syn thesized and investigated are given below.The fundamental and applied interest in studying these compounds is associated with an important feature of these ligands. Thus, these ligands contain two coordina tion sites of different nature, viz., the cyclopentadienyl ring strongly bound to the metal atom and the functional group capable of being involved in the reversible coordi nation. Due to this feature, the ligands are very attractive for the catalyst design, in particular, in the α olefin poly merization, which has stimulated extensive studies in this field from the late 1980s (see the reviews 1-6 ).The presence or absence of the coordination interac tion between the chelating functional group and the metal atom is one of the key factors responsible for the chemi cal, including catalytic, behavior of complexes with side chain functionalized cyclopentadienyl ligands. The coordination ability of chelating heteroatomic functional groups was studied in sufficient detail (primarily by X ray diffraction) for metal complexes in the crystalline state,

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“…To expand our ability to control structure and reactivity, we are aiming for cyclopentadienyl ruthenium complexes with additional intramolecularly tethered coordinating groups [4][5][6][7]. For ruthenium, synthetic approaches to such complexes typically fall into one of two categories: (1) The synthesis of functionalized cyclopentadienes followed by coordination to the metal, or (2) the anchoring of an additional donor ligand to an already formed cyclopentadienyl complex [4][5][6][7][8].…”

Section: Introductionmentioning

confidence: 99%

“…For ruthenium, synthetic approaches to such complexes typically fall into one of two categories: (1) The synthesis of functionalized cyclopentadienes followed by coordination to the metal, or (2) the anchoring of an additional donor ligand to an already formed cyclopentadienyl complex [4][5][6][7][8]. We feel that the latter approach is more versatile albeit less explored [8].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of cyclopentadienyl ruthenium complexes bearing pendant chelating picolinates through an electrophilic precursor

Streu

Carroll

Kohli

et al. 2008

Journal of Organometallic Chemistry

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Aminoethyl-Functionalized Cyclopentadienyl Complexes of d-Block Elements

Cited by 63 publications

References 0 publications

Chelate Complexes of Functionalized Cycloheptatrienyl Ligands: 17- and 18-Electron Molybdenum Complexes with Linked Cycloheptatrienyl−Phosphane Ligands and Their Use in Transition Metal Catalysis

Chelate Complexes of Functionalized Cycloheptatrienyl Ligands: 17- and 18-Electron Molybdenum Complexes with Linked Cycloheptatrienyl−Phosphane Ligands and Their Use in Transition Metal Catalysis

Zirconium and titanium complexes with side-chain functionalized cyclopentadienyl ligands

Synthesis of cyclopentadienyl ruthenium complexes bearing pendant chelating picolinates through an electrophilic precursor

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