Cesium Trialkylfluorometalates of Gallium and Indium:  Compounds with Heterocubane Structure

Werner, Bert; Kräuter, Thomas; Neumüller, Bernhard

doi:10.1021/ic951467r

Cited by 23 publications

(9 citation statements)

References 28 publications

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“…As found by X-ray crystallographic studies, KFÁGaMe 3 forms tetrameric molecular with a cubic core [24][25][26] crystallizing in the cubic space group P43m. The molecular structure of the complex is shown in Fig.…”

Section: Molecular Structuresupporting

confidence: 53%

“…The main structural feature is a slightly distorted ionic K 4 F 4 heterocubane central core, which is comparable topologically with a structural fragment observed in crystalline KF. 24 The arrangement of the methyl groups around the potassium cations with a relatively short K … C distance of 3.455(5) Å indicates weak intermolecular interactions of partly ionic character. 22 The distortion of the K 4 F 4 heterocubane core can be characterized as outward movements of potassium cations along the cube space diagonals, which leads to the formation of butterfly-like cubic faces with torsion angles of K-F-F-K = 168.…”

Section: Molecular Structurementioning

confidence: 99%

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Synthesis and purification of trimethylgallium for MOCVD: molecular structure of (KF)4�4(Me3Ga)

Starowieyski

Chwojnowski

Jankowski

et al. 2000

Appl. Organometal. Chem.

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Trimethylgallium was obtained from a 3:1 molar mixture of Me 2 AlCl (1) and GaCl 3 (2) only in the presence of NaCl. The mechanism of the reaction was traced. It is postulated that the gallium-aluminium dimers Cl n Me 2Àn AlCl 2 GaCl m Me 2Àm (m and n = 0, 1 or 2), formed in consecutive alkylation steps, do not participate in further alkyl-chlorine exchange. NaCl splits the dimers that form the precipitate of Na[Me-AlCl 3 ] (3), thus liberating Me n GaCl 3Àn which, on further alkylation by Me 2 AlCl, finally yields Me 3 Ga. For an MOCVD application, it is purified through a complex with KF, which under vacuum decomposes at 180-300°C, to yield a product contaminated by less than 1 ppm of the total impurities. The X-ray study of the complex reveals a tetrameric, highly symmetrical heterocubane of formula (KF) 4 Á4(Me 3 Ga).

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Section: Molecular Structuresupporting

confidence: 53%

Section: Molecular Structurementioning

confidence: 99%

Synthesis and purification of trimethylgallium for MOCVD: molecular structure of (KF)4�4(Me3Ga)

Starowieyski

Chwojnowski

Jankowski

et al. 2000

Appl. Organometal. Chem.

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“…Only five other transition metal complexes containing a l 4 -F − ligand, as in 3, have been crystallographically characterised, all of which contain d 0 molybdenum(VI), 33 vanadium(V) 34 or titanium(IV) 35 metal ions. A small number of other l 4 -F − com-pounds are also known that contain group 1 or group 2 metals, 36 or a lanthanide ion. 37 Hence, 3 is unique as a l 4 -F − complex containing a late transition ion in a moderate oxidation state.…”

Section: Discussionmentioning

confidence: 99%

Four copper(ii) pyrazolido complexes derived from reactions of 3{5}-substituted pyrazoles with CuF2 or Cu(OH)2

et al. 2007

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Treatment of CuF(2) with 2 equiv of 3{5}-[pyrid-2-yl]pyrazole (Hpz(Py)), 3{5}-phenylpyrazole (Hpz(Ph)) or 3{5}-[4-fluorophenyl]pyrazole (Hpz(PhF)) in MeOH, followed by evaporation to dryness and recrystallisation of the solid residues, allows solvated crystals of [{Cu(micro-pz(Py))(pz(Py))}(2)] (1), [{Cu(micro-pz(Ph))(2)}(4)] (2) and [Cu(4)F(2)(micro(4)-F)(micro-pz(PhF))(5)(Hpz(PhF))(4)] (3) to be isolated in moderate-to-good yields. Similar reactions of these three pyrazoles with Cu(OH)(2) in refluxing MeOH respectively afford 1, 2 and [Cu(pz(PhF))(2)(Hpz(PhF))(2)] (4) in ca. 10% yield. Crystalline 1 x 1/2H(2)O x 2CHCl(3) contains two independent dinuclear molecules with a puckered di-(1,2-pyrazolido) bridge motif, linked by a bridging, hydrogen-bonding water molecule. Compound 2 x 1/2C(5)H(12), containing cyclic, square tetranuclear complex molecules, is the first homoleptic divalent metal pyrazolide to have a discrete molecular rather than polymeric structure, for a metal other than Pd or Pt. The two independent complex molecules in 3 x 3/4CH(2)Cl(2) x Hpz(PhF) contain a unique tetrahedral [Cu(4)(micro(4)-F)](7+) core, three of whose edges are spanned by bridging pyrazolido groups. Magnetic data show that the copper centres in 1 and 3 are antiferromagnetically coupled, but that dried bulk samples of 2 do not retain their molecular structure.

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“…In these cases, phosphorus atom is connected only to one metal center and can exhibit either pyramidal geometry with one lone pair or planar geometry with the lone pair participating in π bonding , . It should be noted that, among the high number of bridged phosphido complexes,, there are many reports of transition metal complexes featuring non‐bridging, terminal phosphido ligands,, including some supported by nacnac ligands . However, only a handful of known terminal phosphido complexes, incorporate iron and, in most cases, these complexes are supported by carbonyl or cyclopentadienyl co‐ligands.…”

Section: Introductionmentioning

confidence: 99%

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

et al. 2018

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We report the synthesis of the first series of terminal phosphido iron complexes supported by a -diketiminato ligand (Dippnacnac) and their catalytic activity in dehydrocoupling of secondary phosphines. Anionic and neutral mono-or diphosphido complexes were obtained from the reaction of [(Dippnacnac)FeCl 2 Li(dme) 2 ] with the R 2 PLi (R = iPr, tBu, Cy, Ph) phosphides by tuning the stoichiometric ratio, polarity of the solvent, and the bulkiness of the substituents at the P-atom. The structures of the synthesized compounds were determined by single-crystal X-ray diffraction, which revealed that the iron [a] Reports by Webster et al. [14,27,43,[98][99][100][101][102] on the use of an iron(II) -diketiminato pre-catalyst, [(Dippnacnac)Fe(CH 2 TMS)] for the hydrophosphination of unsaturated hydrocarbons and dehydrocoupling of primary and secondary phosphines postulated the formation of an intermediate terminal phosphido complex. In the case of hydrophosphination, the authors proposed that the active catalyst is a monomeric phosphido complex; however, the active species was isolated as a bridging complex, [(Dippnacnac)Fe(PRH(CH 2 ) 3 CH=CH 2 )] 2 . [27] Worth emphasizing is that this compound is not only the first -diketiminate iron complex bridged by phosphido groups, but also a perfect example highlighting the catalytic potential of lowcoordinate iron compounds. The hydrophosphination and dehydrocoupling processes are both ideally suited for the synthesis of novel P-containing compounds and their catalytic improvements will expand the access to functionalized phosphines, diphosphanes, and other P-containing derivatives.Recently, we have reported a new synthetic method to access iron(II) phosphanylphosphido complexes using as starting materials the -diketiminato complex [(Dippnacnac)FeCl 2 -Li(dme) 2 ] [103] and lithium salts of diphosphanes, R 2 P-P(SiMe 3 )Li (R = iPr, tBu). [104] Due to the propensity of the diphosphorus ligand to undergo P-P bond cleavage, these iron(II) phosphanylphosphido complexes have rather limited catalytic potential. Considering this limitation, we directed our attention to iron(II) complexes with phosphido R 2 P ligands. In this paper, we detail the syntheses, structures, and spectroscopic characterization of the first series of terminal phosphido Fe II complexes stabilized by -diketiminates. We also discuss their thermal stability and catalytic activity in promoting the dehydrocoupling of secondary phosphines. Reaction of [(Dippnacnac)FeCl 2 ] with Ph 2 PLi:To the suspension of [(Dippnacnac)FeCl 2 ] (0.272 g, 0.5 mmol) in 2.5 mL of solvent (tolu-Eur.

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Cesium Trialkylfluorometalates of Gallium and Indium: Compounds with Heterocubane Structure

Cited by 23 publications

References 28 publications

Synthesis and purification of trimethylgallium for MOCVD: molecular structure of (KF)4�4(Me3Ga)

Synthesis and purification of trimethylgallium for MOCVD: molecular structure of (KF)4�4(Me3Ga)

Four copper(ii) pyrazolido complexes derived from reactions of 3{5}-substituted pyrazoles with CuF2 or Cu(OH)2

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

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