The Molecular Structure of Pentamethylcyclopentadienylgallium, Ga(eta-C5Me5), by Gas-Phase Electron Diffraction. The First Monomeric Organogallium(I) Compound.

Haaland, Arne; Martinsen, Kjell-Gunnar; Volden, Hans V.; Loos, Dagmar; Schnöckel, Hansgeorg; Paulsen, Gudrun B.; Nielsen, Ruby I.; Olsen, Carl Erik; Pedersen, Christian; Stidsen, Carsten E.

doi:10.3891/acta.chem.scand.48-0172

Cited by 71 publications

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“…Although pentamethylcyclopentadienylgallium(I) exists as a hexamer in the crystalline state [10], monomerization is relatively easy in both solution and in the vapour phase [11]. Treatment of an equimolar mixture of Al(C 6 F 5 ) 3 ×toluene and (Z 5 -C 5 Me 5 )Ga units in toluene solution, followed by work-up of the reaction mixture, results in a 62% yield of the colourless, crystalline donor -acceptor complex (Z 5 -C 5 Me 5 )Ga?Al(C 6 F 5 ) 3 1.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and structure of (η⁵-C₅Me₅)Ga→Al(C₆F₅)₃. The first example of a gallium – aluminium bond

Gorden¹,

Macdonald²,

Cowley

2005

Main Group Chemistry

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Section: Resultsmentioning

confidence: 99%

Synthesis and structure of (η⁵-C₅Me₅)Ga→Al(C₆F₅)₃. The first example of a gallium – aluminium bond

Gorden¹,

Macdonald²,

Cowley

2005

Main Group Chemistry

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“…All Cp* moieties are bound to the Ga centers in a nearly ideal symmetric h 5 mode with average values for the Cp* centroid ÀGa bond lengths of 1.999 for the terminal Cp*Ga units and 2.048 for the bridging ligands, both values being close to the free ligand value of 2.081 (gas phase, monomer). [18] The NMR spectra of the dinuclear Pd 2 Ga 5 (1 c) in C 6 D 6 exhibit only one set of signals for the GaCp* ligands ( , that is, a fluxional process is active, exchanging the bridging and terminally coordinated ligands on the NMR timescale. At À80 8C in [D 8 ]toluene the signal splits into two distinguishable resonances (2.07 and 2.03 ppm) with an integral ratio of 2:3 accounting for a structure similar to that observed in the solid state.…”

Section: Resultsmentioning

confidence: 99%

The Clusters [M_a(ECp*)_b] (M=Pd, Pt; E=Al, Ga, In): Structures, Fluxionality, and Ligand Exchange Reactions

Steinke

Gemel

Winter

et al. 2005

Chemistry A European J

100

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The synthesis and structural characterization of the novel homoleptic cluster complexes [Pd2(GaCp*)2(mu2-GaCp*)3] (1c), [Pd3(GaCp*)4(mu2-GaCp*)4] (2b) and [Pd3(AlCp*)2(mu2-AlCp*)2(mu3-AlCp*)2] (3) (Cp*=C5Me5) are presented. Furthermore, ligand exchange reactions of these cluster complexes are explored. In contrast to the electronically and sterically saturated complexes [M(ECp*)4] (M=Ni, Pd, Pt), the new unsaturated analogues [M(a)(ER)b] (E=Al, Ga, In) react with a variety of typical ligands (Cp*Al, CO, phosphines, isonitriles) to give new di- and tri-substituted compounds like [Pt2(GaCp*)2(mu2-AlCp*)3] (1d), [PdPt(GaCp*)(PPh3)(mu2-GaCp*)3] (4b), or [Pd3(PPh3)3(mu2-InCp*)(mu3-InCp*)2] (8). The trends of the reactivity of [M(a)(ER)b] as well as their fluxional behavior in solution has been elucidated by NMR spectroscopy, resulting in a mechanistic rationale for the ligand exchange reactions as well as the fluxional processes.

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“…However, in contrast to the Al-Al distances in the corresponding tetrameric aluminium derivative [Al(h 5 -C 5 Me 5 )] 4 (Dohmeier et al 1991) the E-E distances are rather long and indicate only weak van der Waals Ga-Ga or In-In interactions. Accordingly, complete dissociation occurs in solution or in the gas phase (Haaland et al 1994). …”

Section: Other Single Shell Clusters E N R N Of Aluminium Gallium Anmentioning

confidence: 99%

Tetrahedral homonuclear organoelement clusters and subhalides of aluminium, gallium and indium

Uhl

2004

Naturwissenschaften

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This review is focused on the synthesis and the reactivity of tetrahedral organoelement clusters of the heavier elements of third main-group aluminium, gallium, and indium, which have been known for about a decade. They possess the elements in an unusually low oxidation state of +1 and have direct element--element interactions between their four constituents. Each cluster atom is further attached to one terminal and in most cases a bulky organic substituent, which prevents disproportionation by steric shielding. The synthesis of these compounds succeeds by different methods such as the reduction of suitable organoelement(III) halides with alkali metals and magnesium or the treatment of element(I) halides with lithium organyls. They are deeply coloured, and their bonding situation may best be described by delocalized molecular orbitals. They show a singular chemical reactivity, which results in the formation of many secondary products possessing unprecedented structures and properties. The synthesis of organoelement subhalides still containing the elements in low oxidation states is discussed in more detail in the second part of this review. These compounds are easily accessible by the careful oxidation of the clusters with halogen donors such as hexachloroethane or with AlX(3)/X(2) mixtures. They produce dimers via halogen bridges, but in certain cases monomers were observed even for the solid state. They are very effective starting compounds for secondary reactions and the generation of new products containing the elements in unusual oxidation states by salt-elimination reactions, for instance.

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The Molecular Structure of Pentamethylcyclopentadienylgallium, Ga(eta-C5Me5), by Gas-Phase Electron Diffraction. The First Monomeric Organogallium(I) Compound.

Cited by 71 publications

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Synthesis and structure of (η⁵-C₅Me₅)Ga→Al(C₆F₅)₃. The first example of a gallium – aluminium bond

Synthesis and structure of (η⁵-C₅Me₅)Ga→Al(C₆F₅)₃. The first example of a gallium – aluminium bond

The Clusters [M_a(ECp*)_b] (M=Pd, Pt; E=Al, Ga, In): Structures, Fluxionality, and Ligand Exchange Reactions

Tetrahedral homonuclear organoelement clusters and subhalides of aluminium, gallium and indium

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The Molecular Structure of Pentamethylcyclopentadienylgallium, Ga(eta-C5Me5), by Gas-Phase Electron Diffraction. The First Monomeric Organogallium(I) Compound.

Cited by 71 publications

References 0 publications

Synthesis and structure of (η5-C5Me5)Ga→Al(C6F5)3. The first example of a gallium – aluminium bond

Synthesis and structure of (η5-C5Me5)Ga→Al(C6F5)3. The first example of a gallium – aluminium bond

The Clusters [Ma(ECp*)b] (M=Pd, Pt; E=Al, Ga, In): Structures, Fluxionality, and Ligand Exchange Reactions

Tetrahedral homonuclear organoelement clusters and subhalides of aluminium, gallium and indium

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Synthesis and structure of (η⁵-C₅Me₅)Ga→Al(C₆F₅)₃. The first example of a gallium – aluminium bond

Synthesis and structure of (η⁵-C₅Me₅)Ga→Al(C₆F₅)₃. The first example of a gallium – aluminium bond

The Clusters [M_a(ECp*)_b] (M=Pd, Pt; E=Al, Ga, In): Structures, Fluxionality, and Ligand Exchange Reactions