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Cairns, Kelsey R.
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article
Mono- and di-phosphine oxide complexes of aluminium, gallium and indium with weakly coordinating triflate anions – Synthesis, structures and properties
Abstract
<p>Reaction of the Group 13 triflates, M(OTf)<sub>3</sub> (M = Al, Ga, In; OTf = CF<sub>3</sub>SO<sub>3</sub><sup>−</sup>), with 3 mol. eq. of R<sub>3</sub>PO (R = Ph or Me) gives the six-coordinate complexes, [M(OTf)<sub>3</sub>(R<sub>3</sub>PO)<sub>3</sub>], with coordinated triflate, as white powdered solids. Similarly, using 3 mol. eq. of PyNO (pyridine-N-oxide) readily forms [In(OTf)<sub>3</sub>(PyNO)<sub>3</sub>], whose crystal structure confirms a mer octahedral arrangement. In contrast, reaction of the harder Lewis acids Al(III) and Ga(III) with PyNO produce mixtures, mostly likely of the 3:1 and 4:1 species, [M(OTf)<sub>3</sub>(PyNO)<sub>3</sub>] and [M(OTf)<sub>2</sub>(PyNO)<sub>4</sub>][OTf] (M = Al, Ga). Both of the tetrakis species have been confirmed via single crystal X-ray studies and shown to exist as trans isomers. Higher ratios (4:1, 5:1 and 6:1) of Me<sub>3</sub>PO coordinated to In(OTf)<sub>3</sub> can also be achieved by varying the reaction stoichiometry appropriately, with the coordinated OTf groups readily displaced by the Me<sub>3</sub>PO. Crystal structures of two polymorphs of the salt, [In(OTf)<sub>2</sub>(Me<sub>3</sub>PO)<sub>4</sub>][In{(OH<sub>2</sub>)<sub>2</sub>(OTf)<sub>4</sub>}(Me<sub>3</sub>PO)<sub>4</sub>], in which the [In{(OH<sub>2</sub>)<sub>2</sub>(OTf)<sub>4</sub>}(Me<sub>3</sub>PO)<sub>4</sub>]<sup>−</sup> anion is (unusually) comprised of a ‘In<sup>III</sup>(OH<sub>2</sub>)<sub>2</sub>(Me<sub>3</sub>PO)<sub>4</sub>′ unit with four OTf anions H-bonded to the aquo ligands, giving the overall monoanionic charge. A similar arrangement is present in [In(OTf)<sub>2</sub>(Ph<sub>3</sub>PO)<sub>4</sub>][In{(OH<sub>2</sub>)<sub>4</sub>(OTf)<sub>4</sub>}(Ph<sub>3</sub>PO)<sub>2</sub>], the structure of which shows that all of the H atoms associated with the four aquo ligands in the [In{(OH<sub>2</sub>)<sub>4</sub>(OTf)<sub>4</sub>}(Ph<sub>3</sub>PO)<sub>2</sub>]<sup>−</sup> form significant H-bonds to the OTf groups; specifically, the four OTf<sup>−</sup> anions each show two O⋯H interactions, forming bridges that link the equatorial aquo ligands into a 24-membered ‘pseudo-macrocyclic’ ring. The crystal structure of the mononuclear 5:1 complex, [Ga(Me<sub>3</sub>PO)<sub>5</sub>(MeCN)][OTf]<sub>3</sub>, is also described. Using the diphosphine dioxide, dppmO<sub>2</sub> (Ph<sub>2</sub>P(O)CH<sub>2</sub>P(O)Ph<sub>2</sub>), with M(OTf)<sub>3</sub> in a 3:1 ratio readily affords the tris-chelate species, [M(dppmO<sub>2</sub>)<sub>3</sub>][OTf]<sub>3</sub> for all three metals, while a 2:1 ratio also gives [Ga(OTf)<sub>2</sub>(dppmO<sub>2</sub>)<sub>2</sub>][OTf]. Crystal structures of both [Al(dppmO<sub>2</sub>)<sub>3</sub>][OTf]<sub>3</sub>·MeCN and [Ga(dppmO<sub>2</sub>)<sub>3</sub>][OTf]<sub>3</sub>·2CHCl<sub>3</sub> are reported. Multinuclear (<sup>1</sup>H, <sup>13</sup>C{<sup>1</sup>H}, <sup>19</sup>F{<sup>1</sup>H}, <sup>31</sup>P{<sup>1</sup>H}, <sup>27</sup>Al, <sup>71</sup>Ga and <sup>115</sup>In, where appropriate) NMR data show that in CD<sub>3</sub>CN the complexes are labile and the different R<sub>3</sub>PO coordination environments are not distinguished (although exchange between coordinated and ‘free’ Me<sub>3</sub>PO is slow on the <sup>31</sup>P NMR timescale), while the MeCN solvent also replaces OTf in the metal coordination sphere.</p>