Dataset Information

A one-dimensional bromide-bridged PtII/PtIV mixed-valence complex with a 2-bromo-ethane-sulfonate counter-ion.

ABSTRACT: The title salt, catena-poly[[[bis-(ethyl-enedi-amine)-platinum(II)]-?-bromido-[bis(ethyl-enedi-amine)-platinum(IV)]-?-bromido] tetra-kis-(2-bromo-ethane-sulfon-ate) dihydrate], {[PtIIPtIVBr2(C2H8N2)4](C2H4BrSO3)4·2H2O} n , crystallizes in the space group P21212. It has a linear chain structure extending parallel to the c axis, composed of square-planar [Pt(en)2]2+ and elongated octa-hedral trans-[PtBr2(en)2]2+ cations (en is ethyl-enedi-amine) stacked alternately and bridged by the Br atoms. The Pt site of the [PtII/IV(en)2] unit is located on a general position. The Br site, which is also located on a general position, is equally disordered over two positions. The Pt and Br atoms form a slight zigzag ?Br-PtIV-Br?PtII? chain, with PtIV-Br bond lengths of 2.453?(2) and 2.491?(3)?Å, PtII?Br contacts of 3.069?(2) and 3.032?(3)?Å, and PtIV-Br?PtII angles of 178.06?(13) and 177.70?(13)°. The mixed-valence state of the Pt site is expressed by the parameter ? = (PtIV-Br)/(PtII?Br), with values of 0.799 and 0.822 for the two independent Br atoms. In the crystal, N-H?O and O-H?O hydrogen bonds between the amine groups of the Pt complex chains, the sulfonate groups and water mol-ecules of crystallization, stabilize the cationic columnar structure.

SUBMITTER: Matsushita N

PROVIDER: S-EPMC5598828 | biostudies-literature | 2017 Jul

REPOSITORIES: biostudies-literature

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A one-dimensional bromide-bridged PtII/PtIV mixed-valence complex with a 2-bromo-ethane-sulfonate counter-ion.

Matsushita Nobuyuki N Taira Ayako A Taoka Yoshiya Y

Acta crystallographica. Section E, Crystallographic communications 20170704 Pt 8

The title salt, catena-poly[[[bis-(ethyl-enedi-amine)-platinum(II)]-μ-bromido-[bis(ethyl-enedi-amine)-platinum(IV)]-μ-bromido] tetra-kis-(2-bromo-ethane-sulfon-ate) dihydrate], {[PtIIPtIVBr2(C2H8N2)4](C2H4BrSO3)4·2H2O} n , crystallizes in the space group P21212. It has a linear chain structure extending parallel ...[more]

PMID: 28932416

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Project description:The oxo- and catecholate-bridged UIV/UIV Pacman complex [{(py)UIVOUIV(μ-O2C6H4)(py)}(LA)] A (LA = a macrocyclic "Pacman" ligand; anthracenylene hinge between N4-donor pockets, ethyl substituents on meso-carbon atom of each N4-donor pocket) featuring a bent UIV-O-UIV oxo bridge readily reacts with small molecule substrates to undergo either oxo-atom functionalisation or substitution. Complex A reacts with H2O or MeOH to afford [{(py)UIV(μ-OH)2UIV(μ-O2C6H4)(py)}(LA)] (1) and [{(py)UIV(μ-OH)(μ-OMe)UIV(μ-O2C6H4)(py)}(LA)] (2), respectively, in which the bridging oxo ligand in A is substituted for two bridging hydroxo ligands or one bridging hydroxo and one bridging methoxy ligand, respectively. Alternatively, A reacts with either 0.5 equiv. of S8 or 4 equiv. of Se to provide [{(py)UIV(μ-η2:η2-E2)UIV(μ-O2C6H4)(py)}(LA)] (E = S (3), Se (4)) respectively, in which the [E2]2- ion bridges the two UIV centres. To the best of our knowledge, complex A is the first example of either a d- or f-block bimetallic μ-oxo complex that activates elemental chalcogens. Complex A also reacts with XeF2 or 2 equiv. of Me3SiCl to provide [{(py)UIV(μ-X)2UIV(μ-O2C6H4)(py)}(LA)] (X = F (5), Cl (6)), in which the oxo ligand has been substituted for two bridging halido ligands. Reacting A with either XeF2 or Me3SiCl in the presence of O(Bcat)2 at room temperature forms [{(py)UIV(μ-X)(μ-OBcat)UIV(μ-O2C6H4)(py)}(LA)] (X = F (5A), Cl (6A)), which upon heating to 80 °C is converted to 5 and 6, respectively. In order to probe the importance of the bent UIV-O-UIV motif in A on the observed reactivity, the bis(boroxido)-UIV/UIV complex, [{(py)(pinBO)UIVOUIV(OBpin)(py)}(LA)] (B), featuring a linear UIV-O-UIV bond angle was treated with H2O and Me3SiCl. Complex B reacts with two equiv. of either H2O or Me3SiCl to provide [{(py)HOUIVOUIVOH(py)}(LA)] (7) and [{(py)ClUIVOUIVCl(py)}(LA)] (8), respectively, in which reactions occur preferentially at the boroxido ligands, with the μ-oxo ligand unchanged. The formal UIV oxidation state is retained in all of the products 1-8, and selective reactions at the bridging oxo ligand in A is facilitated by: (1) its highly nucleophilic character which is a result of a non-linear UIV-O-UIV bond angle causing an increase in U-O bond covalency and localisation of the lone pairs of electrons on the μ-oxo group, and (2) the presence of the bridging catecholate ligand, which destabilises a linear oxo-bridging geometry and stabilises the resulting products.

Dataset Information

A one-dimensional bromide-bridged PtII/PtIV mixed-valence complex with a 2-bromo-ethane-sulfonate counter-ion.

Publications

A one-dimensional bromide-bridged Pt<sup>II</sup>/Pt<sup>IV</sup> mixed-valence complex with a 2-bromo-ethane-sulfonate counter-ion.

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