Structure and Reactivity of Distanna[2]metallocenophanes of Ruthenium and Osmium

Braunschweig, Holger; Hupp, Florian; Krämer, Thomas; Mager, Julian

doi:10.1021/ic4012247

Cited by 6 publications

(4 citation statements)

References 56 publications

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“…More recently, our group reported on the synthesis of another distanna[2]ferrocenophane via a double salt elimination reaction of 1,1′-dilithioferrocene and t Bu 4 Sn 2 Cl 2 (Scheme ) . In the same manner we were able to synthesize and study distanna[2]metallocenophanes of osmium and ruthenium …”

Section: Introductionmentioning

confidence: 88%

Synthesis and Structure of Group IV Distanna[2]metallocenophanes

et al. 2013

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1,2-Dichloro-1,1,2,2-tetra-tert-butyldistannane reacts with 2 equiv of sodium cyclopentadienide to give a bis(cyclopentadienyl)distannane. Subsequent dilithiation with lithium diisopropylamide and reactions with suitable metal halides yield [(C5H4SntBu2)2MCl2] (M = Ti, Zr, Hf). The group 4 ansa-metallocenes have all been fully characterized by means of multinuclear NMR spectroscopy, elemental analysis, and X-ray diffraction.

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Section: Introductionmentioning

confidence: 88%

Synthesis and Structure of Group IV Distanna[2]metallocenophanes

et al. 2013

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“…In addition to these symmetrically carbon-bridged sandwich compounds, heteroatom-bridged [2]FCPs are known for a variety of elements (B, Si, Ge, − , Sn, , P). Compared to these ferrocene derivatives, significantly fewer examples are known for ruthenium; that is, [2]ruthenocenophanes are known with carbon, ,,, silicon, , and tin in bridging positions. The only [2]osmocenophanes known to date were equipped with either a Si 2 Me 4 or a Sn 2 t Bu 4 linkage …”

Section: Introductionmentioning

confidence: 99%

“…Compared to these ferrocene derivatives, significantly fewer examples are known for ruthenium; that is, [2]ruthenocenophanes are known with carbon, ,,, silicon, , and tin in bridging positions. The only [2]osmocenophanes known to date were equipped with either a Si 2 Me 4 or a Sn 2 t Bu 4 linkage …”

Section: Introductionmentioning

confidence: 99%

[2]Ferrocenophanes with Nitrogen in Bridging Positions

2015

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Three [2]ferrocenophanes ([2]FCPs) bridged by nitrogen and silicon (7 SiMe2 ) and nitrogen and tin (7 SnMe2 , 7 SntBu2 ) were synthesized by salt metathesis between a dilithioferrocene derivative, prepared in situ from 1-bromo-1′-(trimethylsilylamino)ferrocene (6), and Me 2 SiCl 2 , Me 2 SnCl 2 , and tBu 2 SnCl 2 , respectively. A multistep synthesis of precursor 6 is described. Only 7 SiMe2 and 7 SntBu2 could be prepared as analytically pure compounds. The molecular structures of all three [2]FCPs were determined by single-crystal X-ray analysis. Expectedly, the tilting of the Cp ligands in the silicon species 7 SiMe2 is larger [α = 15.73(13)°] than in the tin compounds 7 SnMe2 [α = 9.36(17) and 9.45(18)°] and 7 SntBu2 [α = 10.13(11)°]. Ring-opening polymerizations of 7 SiMe2 and 7 SntBu2 were attempted using the common methods of thermal, transition-metal-catalyzed, anionic, and photocontrolled ring-opening polymerization, but none of the experiments gave polymeric materials.

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“…To date, heterobimetallic [ n ]metallocenophanes (or related species) have been synthesized containing a variety of different metal combinations. , Despite the relative abundance of monometallic monomers, many species are unstrained and, therefore, cannot undergo ROP. Nonetheless, some species have been shown to afford metallic films directly from thermolysis of the monomeric precursor …”

Section: Introductionmentioning

confidence: 99%

Facile Formation of FePd Nanoparticles from Single-Source [1]Ferrocenophane Precursors

et al. 2014

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Mixed-metal FePd alloy nanoparticles (NPs) have been synthesized in moderate yield (ca. 55−60%) and at relatively low temperatures from single-source [1]-ferrocenophane precursors. Thermolysis of [Fe(η 5 -C 5 H 4 ) 2 Pd-(PnBu 3 ) 2 ] (7) (1 h, 150°C) and the new species [Fe(η 5 -C 5 H 4 ) 2 Pd{PnBu 2 (CH 2 ) 4 PnBu 2 }] (9) (1 h, 190°C) afforded crystalline, heterobimetallic FePd alloy NPs with diameters of ca. 4 nm (11) and 3.5 nm (12), respectively, together with mixtures of unidentified, mainly ligand-derived products. Both sets of particles were analyzed by high resolution transmission electron microscopy, which, in addition to providing particle size, determined the spacing between the lattice fringes to be 0.23 nm. Evidence for the formation of alloy nanoparticles, rather than a mixture of those comprising pure metals, was obtained by energy-dispersive X-ray analysis, which confirmed the presence of both Fe and Pd in a single particle. This assertation was further supported by wide-angle X-ray scattering of 11 and 12, which displayed broad reflections at 2θ = 40.58°and 40.09°, respectively, in good agreement with previous studies of FePd NPs. Atomic absorption spectroscopy was employed for bulk analysis of the particles and indicated that that the compositions of 11 and 12 were ca. Fe 35 Pd 65 . ■ INTRODUCTIONObjects with nanoscale dimensions have potential applications in the fields of physics, electrical engineering, and cellular biology due to the unique physical properties that they exhibit. 1 The combination of two or more metals into the mixed-alloy crystalline nanodomain of heterobimetallic NPs can afford species with enhanced magnetic, 2 optical, 3 and electronic 4 properties, relative to their monometallic counterparts. Heterobimetallic NPs have thus been employed in a variety of applications, including catalysis, 5 magnetic data storage, 6,2a environmental remediation, 7 and in fuel cell devices. 4,8 Common methods for the synthesis of heterobimetallic nanoparticles include the co-reduction of metal salts, 9 thermal decomposition, 2a,10 and galvanic replacement reactions. 11 Metallopolymers, where the metal centers are located in the main chain or pendant side group, 12 are attractive precursors to both metal NPs, 13 and magnetic ceramics. 14 Thermolysis of metallopolymers can afford NPs that are stabilized in a ceramic matrix and are thus prevented from aggregating. Furthermore, polymeric precursors can often be cross-linked prior to pyrolysis, enabling ceramic yields to be maximized. 14a,c Significantly, the propensity for metalloblock copolymers to form spatially segregated nanodomains, in both the bulk and solution state, 15 facilitates the formation of nanoparticles in ordered arrays. 16,14e The incorporation of a second metal center into the repeat unit of the polymer (e.g., 1, Figure 1) 13d can facilitate heterobimetallic NP synthesis from polymeric singlesource precursors. 17 Thermal treatment of [n]metallocenophanes (4) usually induces ring-opening polymerization (ROP) to afford po...

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Structure and Reactivity of Distanna[2]metallocenophanes of Ruthenium and Osmium

Cited by 6 publications

References 56 publications

Synthesis and Structure of Group IV Distanna[2]metallocenophanes

Synthesis and Structure of Group IV Distanna[2]metallocenophanes

[2]Ferrocenophanes with Nitrogen in Bridging Positions

Facile Formation of FePd Nanoparticles from Single-Source [1]Ferrocenophane Precursors

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