A New Coordination Mode for the Tripodal [Te(NtBu)3]2− Dianion: Preparation and Structures of {ClIn[Te(NtBu)3]}2 and {LiIn[Te(NtBu)3]2}·LiCl

Chivers, Tristram; Schatte, Gabriele

doi:10.1002/1099-0682(200209)2002:9<2266::aid-ejic2266>3.0.co;2-d

Cited by 5 publications

(2 citation statements)

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“…O involved a spirocyclic indium centre bis(N,NЈ-chelated) by two [Te(NBu t ) 3 ] ions. 138 A new indium phosphate, (NH 4 )In(OH)PO 4 , has been prepared by a hydrothermal reaction and characterised by two independent groups of researchers, both of whom conducted a single crystal X-ray structure determination and luckily arrived at the same conclusions! 139, 140 Zeolites, in which indium has been incorporated along with hydrogen sulfide contain In 2 S, InSH, absorbed H 2 S, and (In 5 ) 7ϩ clusters.…”

Section: Indiummentioning

confidence: 99%

4 Aluminium, gallium, indium, and thallium

Maher

2003

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

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The chemistry of metalloid cluster compounds for Al, Ga and In dominate current Group 13 chemistry; a review by Schnepf and Schnöckel summarizes the situation for Al and Ga. 13b The first direct observation of radicals by EPR in the activation of a Zeigler-Natta system is both interesting and important for our understanding of these catalysts. 50b For gallium and indium chemistry, a highlight very much in tune with the green chemistry movement, is the report of the first aqueous preparation of high yield, relatively monodisperse, well crystallized GaP and InP nanocrystallites, exhibiting pronounced quantum confinement. 59 Whilst they have had to be relegated to ESI, the increasing interest in indium for Barbier-Grignard type organic syntheses in aqueous media has a green complexion and there are the first signs of similar developments for aqueous gallium chemistry. 110b New work on the two-electron transfer for Tl aq 3ϩ /Tl aq ϩ with electrochemical evidence for [Tl()-Tl()] 4ϩ is a major highlight for thallium chemistry. 142 The synthesis and structure of [In()-In()] 4ϩ is also notable. 129 * Electronic supplementary information (ESI) available. See

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Section: Indiummentioning

confidence: 99%

4 Aluminium, gallium, indium, and thallium

Maher

2003

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

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“…The materials have been prepared from the reaction of {Li 2 [Te(NBu t ) 3 ]} 2 and InCl 3 . 42 The reaction of Bu t NTe(µ-NBu t ) 2 TeNBu t with ClSb(µ-NBu t ) 2 SbCl affords the complex {[Bu t NSb(µ-NBu t ) 2 TeNBu t ](µ3-SbCl)}[Cl], probably via the cycloaddition of the diimide monomer Bu t NTeNBu t to the dimer ClSb(µ-NBu t ) 2 SbCl. The complex can also be prepared from the treatment of {Li 2 [Te(NBu t ) 3 ]} 2 with SbCl 3 , but both preparative methods afford Cl 2 Te(µ-NBu t ) 2 Sb[N(H)Bu t ] as the side product.…”

mentioning

confidence: 99%

7 Oxygen, sulfur, selenium and tellurium

Skabara

2003

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

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This chapter reviews original highlights in the chemistry of the Group 16 elements reported during 2002. The bulk of the review focuses on the chemistry/interaction of the chalcogens with other p-block elements. Due to the vast abundance and diversity of research into chalcogen chemistry, the report has been limited to materials with discrete molecular structure, either as novel products or reagents, or obtained by new synthetic strategies. The most important advances in 2002 include the isolation of hitherto unknown functionalities or bonding modes 28,56,60,64 and unusual, unique or unexpected structures. 53,63,79,81 Sulfur, selenium and telluriumAs in previous years, we start by looking at the ability of the heavier chalcogens to form compounds with other p-block elements, and do so by working from left to right across the periodic table starting with Group 13. The preparation of crystalline thioboric acid, (HBS 2 ) 3 , involves the reaction of hydrogen sulfide gas bubbled through molten B 2 S 3 at 500 ЊC. 1 The experimental procedure has several advantages over previous methodologies (e.g. higher purity, lower reaction temperatures) and the material is an important precursor to thioborate glasses and polycrystals. Studies on chalcogen-containing boron clusters included: the S-alkylation and S-amination of methyl thioethers of closo-[B 12 H 12 ] Ϫ derivatives as potential materials for boron neutron capture therapy of cancer; 2 the structural analysis by microwave spectroscopy and quantum chemical calculations of 1-thia-closo-decaborane( 9), 1-SB 9 H 9 ; 3 the single crystal X-ray characterisation of three dinuclear half-sandwich complexes containing bridging dicarba-closo-dodecaboranes:A two-coordinate thallium compound {[Me 2 Si(µ-N t Bu) 2 P᎐ ᎐ S(NPh)-κN-κS]Tl} and two tetrahedral aluminium complexes {[Me 2 Si(µ-N t Bu) 2 P᎐ ᎐ S(NPh)-κN-κE ]AlMe 2 } and {[Me 2 Si(µ-N t Bu) 2 P᎐ ᎐ Se(NPh)-κN-κE ]AlMe 2 } have been synthesised from the reaction of P-anilino-P-chalcogeno(imino)diazasilaphosphetidines and thallium monochloride and trimethylaluminium. 5 The first X-ray crystal structures of homoleptic aluminium alkanethiolate complexes have been reported; [Al(µ-SR)-(SR) 2 ] 2 (R = t-Bu and i-Pr) were prepared from the reactions of NaCSMe 3 with AlBr 3

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Polyimido Uranium(IV) Clusters: Imidometalates with an M₇(μ₃‐N)₆(μ₂‐N)₆ Core Analogous to the Anderson‐Type Polyoxometalate Motif

2008

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Much recent work has been directed to the construction of polyoxo actinide clusters, which are of broad interest for their relevance in the nuclear industry and the natural environment as well as in the field of materials and catalysis. [1][2][3][4] The variety and scope of such polynuclear compounds should be considerably enlarged by replacing the oxo group O 2À with the isoelectronic imido group RN 2À. Novel structures, reactions, and physicochemical properties should emerge, which would be strongly influenced and controlled by the nature of the organic substituent R. [5][6][7] In stark contrast to the large number of imido complexes of the main groups and d transition metals, such compounds of the f elements are much less common. In the lanthanide series, there is only one terminal imido complex, [8] while the few others are di-and tetranuclear compounds in which the NR groups act as bridging or capping ligands.[9] The inverse situation is observed with the imido uranium compounds, since several mononuclear bis(cyclopentadienyl) complexes in the oxidation states + 4, + 5, or + 6 were prepared [10] as well as the imido analogues of the uranyl ion, [U(NR) 2 ] 2+ and [U(NR)(O)]2+ .[11] Structural comparisons, reactivity studies, and theoretical calculations indicate that the UÀN bonds have a more covalent character than the corresponding U À O bonds.[11] Polynuclear uranium imido complexes are scarce; they are limited to a few dimeric, dinuclear derivatives, [12] such as [{(MeC 5 H 4 ) 2 U(m-NR)} 2 ] (R = Ph or SiMe 3 ).[12a] Herein we present the synthesis and X-ray crystal structures of novel uranium clusters in which four or seven metal centers are linked by m 2 -and m 3 -imido ligands and which exhibit unprecedented frameworks.Our initial objective was to prepare an imido analogue of a polyoxo uranium cluster containing the U 6 (m 3 -O) 8 core, in which the uranium atoms were found in the + 4 and/or + 5 oxidation state, [2,4] by following the strategy developed by Power and co-workers, that is, the introduction of the RN 2À group by means of the imide transfer Grignard reagent [{PhNMg(thf)} 6 ].[13] Reaction of six equivalents of UCl 4 and 8/ 6 equivalents of the hexameric magnesium imide in pyridine at 20 8C led to the reproducible formation of the tetranuclear [U 4 (NPh) 6 Cl 4 (py) 8 ] (1, py = pyridine), which was deposited as dark brown crystals of the solvate 1·2 py upon slow diffusion of pentane into the pyridine solution; dark brown crystals of 1·2 py and [U 4 (NPh) 6 Cl 4 (py) 6 ] (2) were obtained after two days when the reaction mixture was heated under reflux. Changing the pyridine solvent to thf has a dramatic influence on both the aggregation process and the structure of the products, since brown crystals of the heptanuclear compounds [Mg(thf) 12 Cl 5 (thf) 6 ]·2 thf (4·2 thf) were deposited from the orange solution after heating at reflux for three days. The tetra-and heptanuclear complexes were synthesized on a preparative scale by using the right stoichiometry of reactants, according to E...

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A New Coordination Mode for the Tripodal [Te(NtBu)3]2− Dianion: Preparation and Structures of {ClIn[Te(NtBu)3]}2 and {LiIn[Te(NtBu)3]2}·LiCl

Cited by 5 publications

References 21 publications

4 Aluminium, gallium, indium, and thallium

4 Aluminium, gallium, indium, and thallium

7 Oxygen, sulfur, selenium and tellurium

Polyimido Uranium(IV) Clusters: Imidometalates with an M₇(μ₃‐N)₆(μ₂‐N)₆ Core Analogous to the Anderson‐Type Polyoxometalate Motif

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A New Coordination Mode for the Tripodal [Te(NtBu)3]2− Dianion: Preparation and Structures of {ClIn[Te(NtBu)3]}2 and {LiIn[Te(NtBu)3]2}·LiCl

Cited by 5 publications

References 21 publications

4 Aluminium, gallium, indium, and thallium

4 Aluminium, gallium, indium, and thallium

7 Oxygen, sulfur, selenium and tellurium

Polyimido Uranium(IV) Clusters: Imidometalates with an M7(μ3‐N)6(μ2‐N)6 Core Analogous to the Anderson‐Type Polyoxometalate Motif

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Polyimido Uranium(IV) Clusters: Imidometalates with an M₇(μ₃‐N)₆(μ₂‐N)₆ Core Analogous to the Anderson‐Type Polyoxometalate Motif