Synthesis of Manganese and Rhenium Half-Sandwich Complexes with Cp-Phosphaferrocene Ligands

Bitta, Joachim; Fassbender, Stefan; Reiß, Guido J.; Frank, and Walter; Ganter, C.

doi:10.1021/om050412m

Cited by 14 publications

(3 citation statements)

References 34 publications

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“…13,[15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] Complexes with two different substituents at phosphorus are comparatively rare. The few, in some cases rather special examples of such complexes, have been reported by Nakazawa and Miyoshi et al (Zr, Hf), [31][32][33] Hey-Hawkins et al (Ti, Zr), 34 Ganter et al (Mn, Ru), [35][36][37] and Saunders et al (Rh). [38][39][40][41] Different substituents at phosphorus render the complexes less symmetric and are expected to affect the chemical and spectroscopic properties of the complexes as well as the energy of activation of an ethene rotation, which has earlier been reported for 2.…”

Section: Introductionmentioning

confidence: 90%

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New cyclopentadienylethylphosphane chelate complexes with unsymmetrical phosphane substitution

Janssen

Butenschön

2011

New J. Chem.

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The syntheses, characterization, and some reactions of (phosphanylethyl)cyclopentadienyl chelate complexes of cobalt, rhodium, iridium, nickel, and chromium with unsymmetrical substitution at the phosphorus atom are described. The ligand systems were prepared by nucleophilic ring opening of spiro[2.4]hepta-4,6-diene with lithium tert-butylphenylphosphide or lithium tert-butylcyclohexylphosphide. The anionic ligands give the respective chelate complexes by treatment with metal halide reagents. In three cases it was possible to obtain X-ray crystal structure analyses. The cobalt chelate complex undergoes oxidative addition with a dihydrosilane, the reaction results in the formation of products with three stereogenic centers at phosphorus, cobalt, and silicon, which show dynamic behavior as indicated by VTNMR. The rhodium chelate complex undergoes oxidative addition of iodomethane with diastereoselective formation of the respective Rh(III) chelate. While diastereoselectivity caused by a planar chiral indenyl ligand or by a stereogenic carbon center in the chelate backbone has earlier been observed, this is the first case of a stereoinduction by the stereogenic phosphorus ligand. Activation energies for the rotation of cobalt and rhodium chelates have also been determined by VTNMR.

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Section: Introductionmentioning

confidence: 90%

“…IR: v˜= 3092 (w), 3055 (w), 2959 (w, C-H), 2361 (w), 1474 (m, C-H), 1435 (m, P-Ph), 1366 (m, t-Bu), 1172 (m), 1100 (m), 1053 (w), 892 (w), 819 (m), 810 (s, Cp), 747 (s, Cp), 699 (s) cm À1 . MS: m/z (%) = 379 (30) [M + ], 288 (54), 286 (100), 202 (44), 124 (26), 109 (37), 91 (36), 57 (76)…”

Section: Chloro-{g 5 :G 1 [2-(tert-butylcyclohexylphosphanyl)ethyl]-c...mentioning

confidence: 99%

New cyclopentadienylethylphosphane chelate complexes with unsymmetrical phosphane substitution

Janssen

Butenschön

2011

New J. Chem.

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“…81 A phosphaferrocene-substituted cyclopentadienyl anion has been used to synthesise novel manganese and rhenium tricarbonyl half-sandwich complexes. 82 These complexes transform to dicarbonyl complexes upon irradiation, with phosphaferrocene donor groups coordinated in an intramolecular chelating manner. Fac-[Re(bipy)(CO 3 )(PR 3 )] + (PR 3 = trialkyl-or triarylphosphines) (7) has been used to study the effect of intramolecular p-p and CH-p interactions between ligands on the spectroscopic, electrochemical and structural properties of the complex.…”

Section: Rheniummentioning

confidence: 99%

Manganese, technetium and rhenium

West

2006

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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The first complex containing three-coordinate manganese(I) that contains a Mn-Mn bond has been reported. The compound was synthesised by reduction of a bis(m-iodo)dimanganese(II) complex, and exhibits unusual magnetic properties and an antiferromagnetic interaction between the metal centres. A novel glucosamine-dipicolylamine conjugate of 99m Tc(I) has been prepared. This complex has ideal properties for therapeutic applications as it is easily characterised, stable and kinetically inert and contains an N-functionalised glucosamine, a carbohydrate derivative that has been shown to accumulate in tumours. A sterically demanding, soluble rhenium m 2 -pyrazolate complex has been synthesised and shown to be active in catalysis. The complex was successfully used in the oxidation of triphenylphosphine and the epoxidation of cyclooctene, with very high catalytic rates being observed.

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Hybrid Ligands with N‐Heterocyclic Carbene and Chiral Phosphaferrocene Components

Willms

Frank

Ganter

2008

Chemistry A European J

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N-Heterocyclic carbenes (NHCs) possessing one or two 3,4-dimethylphosphaferrocenyl substituents and either methylene or ethylene alkyl bridges have been prepared. These carbenes turned out to be remarkably stable and were characterized by NMR methods and partly by mass spectrometry. Their molybdenum and ruthenium complexes were examined in order to determine the electronic properties and the coordination behaviour of these chiral PC- and PCP-chelate ligands, which combine a NHC unit as a strong sigma-donor with pi-accepting phosphaferrocene moieties. Crystal structures of one ligand precursor and of three complexes have been determined.

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Synthesis of Manganese and Rhenium Half-Sandwich Complexes with Cp-Phosphaferrocene Ligands

Cited by 14 publications

References 34 publications

New cyclopentadienylethylphosphane chelate complexes with unsymmetrical phosphane substitution

New cyclopentadienylethylphosphane chelate complexes with unsymmetrical phosphane substitution

Manganese, technetium and rhenium

Hybrid Ligands with N‐Heterocyclic Carbene and Chiral Phosphaferrocene Components

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