Π-Bonding IN INORGANIC COMPOUNDS: III. A MAGNETOCHEMICAL STUDY OF HEXAHALOOSMATES AND HEXACHLORORHENATE

Westland, Alan D.; Bhiwandker, N. C.

doi:10.1139/v61-162

Cited by 24 publications

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“…Hexahalorhenate(IV) salts are among the first examples of magnetic studies on rhenium(IV) complexes. − The investigations of the magnetic properties of different ionic salts containing the [ReX 6 ] 2- anion (X = F, Cl, Br, or I) which were carried out by several research groups in the temperature range 80−300 K suggested the occurrence of large antiferromagnetic interactions between the paramagnetic Re(IV) centers (three unpaired electrons on each rhenium atom). − Figgis et al pointed out that the magnetic exchange in these systems depends on the tendency of the metal electrons to be transferred to the X ligand and on the X···X separation between the anions in the lattice. In this sense, they found that the antiferromagnetic interaction on different [ReCl 6 ] 2- salts can be related with the size of the cation, and that the magnitude of the magnetic coupling for the potassium and cesium salts of [ReX 6 ] 2- increases in the order F < Cl < Br < I, even when different crystal structures of the ionic salts are involved.…”

Section: Introductionmentioning

confidence: 99%

Magnetic Studies on Hexaiodorhenate(IV) Salts of Univalent Cations. Spin Canting and Magnetic Ordering in K₂[ReI₆] withT_c= 24 K

et al. 2003

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The ionic salts of rhenium(IV) of formula (Cat)(2)[ReI(6)] with Cat = Li(+) (1), Na(+) (2), K(+) (3), Rb(+) (4), Cs(+) (5), NH(4)(+) (6), and AsPh(4)(+) (7) [AsPh(4)(+) = tetraphenylarsonium cation] have been synthesized, and the structures of two of them (namely, 3 and 6) were determined by single-crystal X-ray diffraction. 3 crystallizes in the monoclinic system, space group Pn, with a = 7.815(1) A, b = 7.874(1) A, c = 11.335(1) A, beta = 90.38(1) degrees, and Z = 2 whereas 6 crystallizes in the tetragonal system, space group P4/mnc, with a = 7.881(1) A, b = 7.881(1) A, c = 11.474(2) A, and Z = 2. The structures of 3 and 6 are made up of discrete [ReI(6)](2)(-) anions and K(+) (3) or NH(4)(+) (6) cations held together by electrostatic forces (3 and 6) and N-H.I hydrogen bonds (6). The rhenium(IV) cation in 3 and 6 is surrounded by six iodide ligands in an octahedral environment with the Re-I bond lengths varying in a very narrow range [2.704(3)-2.738(3) and 2.716(1)-2.722(2) A for 3 and 6, respectively]. The [ReI(6)](2)(-) anions in 6 describe a tetragonally distorted body-centered cubic structure. In 3, the arrangement of these units is similar but more distorted. The different arrangement of the anions in 3 and 6 accounts for the centrosymmetric (6) and non-centrosymmetric (3) structures observed. The magnetic properties of 1-7 were investigated in the temperature range 2.0-300 K. The magnetic behavior of 7 is that of a magnetically diluted Re(IV) complex with a large value of the zero-field splitting of the ground level (|2D| = 49.8 cm(-)(1)) whereas those of 1, 2, and 4-6 are typical of antiferromagnetically coupled systems with susceptibility maxima at 28 (1), 27 (2), 21 (4), 16 (5), and 20 K (6). In the case of compound 3, its magnetic behavior in the high-temperature range is parallel to that observed in the parent salts but below 24 K it is a weak ferromagnet with a canting angle of ca. 1.2 degrees.

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Section: Introductionmentioning

confidence: 99%

Magnetic Studies on Hexaiodorhenate(IV) Salts of Univalent Cations. Spin Canting and Magnetic Ordering in K₂[ReI₆] withT_c= 24 K

et al. 2003

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“…In a previous publication (3) it was shown that there is extellsive superexchange ill IC20sC16, Ii20sBrG, and IC2ReC1G. 'rl~is apparently operates through d,-/I, bonding orbitals which encompass the metal atom and its ligands a n d , as well, p,-p, overlap between the ligands of the neighboring complex groups (4).…”

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confidence: 99%

Π-Bonding IN INORGANIC COMPOUNDS: IV. ROLE OF UNPAIRED ELECTRONS IN HEXAHALO COMPLEXES

Westland¹,

Bhiwandker²

1961

Can. J. Chem.

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A s t~~d y of ds-p, bonding in paramagnetic compounds having thc potassium chloroplatinate structi~re is dcscribed. I t is shown t h a t the magnetic supereschangc effect is approximately proportional to the numl~cr of unpaired electrons i n t.,%a~lcl t. , " systelns b~~t there is a n irregnlarity in the kO3 system of p o t a s s i~~m chlororhenatc. This singularity of the t?,3 casc is consiclerecl to be a result of thc orbital alacl crystal symmetries. T h c magnetic properties of the compouncls are related to the extent of T-bonding stabilization in octahetlral complcscs having various configurations tr," on their central atoms.

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“…They were determined on a modified Chevenard thermobalance in a nitrogen atmosphere as described elsewhere. 8 In a separate run a sample of Zn2(IDP)(CgHgPOg)2 was taken to constant weight at 350°. Anal.…”

Section: Methodsmentioning

confidence: 99%

Inorganic Coördination Polymers. V. The Use of Neutral Ligands

Block¹,

Simkin²

1963

Inorg. Chem.

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Π-Bonding IN INORGANIC COMPOUNDS: III. A MAGNETOCHEMICAL STUDY OF HEXAHALOOSMATES AND HEXACHLORORHENATE

Abstract: The anonialously small magnetic niornents of o s n~i~~n~ ( l V ) and rhenium(1V) in their hexahalo complexes are investigated by measurement of the magnetic susceptibilities of the mixed crystal systems, 1 Show more

Cited by 24 publications

References 5 publications

Magnetic Studies on Hexaiodorhenate(IV) Salts of Univalent Cations. Spin Canting and Magnetic Ordering in K₂[ReI₆] withT_c= 24 K

Magnetic Studies on Hexaiodorhenate(IV) Salts of Univalent Cations. Spin Canting and Magnetic Ordering in K₂[ReI₆] withT_c= 24 K

Π-Bonding IN INORGANIC COMPOUNDS: IV. ROLE OF UNPAIRED ELECTRONS IN HEXAHALO COMPLEXES

Inorganic Coördination Polymers. V. The Use of Neutral Ligands

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Π-Bonding IN INORGANIC COMPOUNDS: III. A MAGNETOCHEMICAL STUDY OF HEXAHALOOSMATES AND HEXACHLORORHENATE

Abstract: The anonialously small magnetic niornents of o s n~i~~n~ ( l V ) and rhenium(1V) in their hexahalo complexes are investigated by measurement of the magnetic susceptibilities of the mixed crystal systems, 1 Show more

Cited by 24 publications

References 5 publications

Magnetic Studies on Hexaiodorhenate(IV) Salts of Univalent Cations. Spin Canting and Magnetic Ordering in K2[ReI6] withTc= 24 K

Magnetic Studies on Hexaiodorhenate(IV) Salts of Univalent Cations. Spin Canting and Magnetic Ordering in K2[ReI6] withTc= 24 K

Π-Bonding IN INORGANIC COMPOUNDS: IV. ROLE OF UNPAIRED ELECTRONS IN HEXAHALO COMPLEXES

Inorganic Coördination Polymers. V. The Use of Neutral Ligands

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Magnetic Studies on Hexaiodorhenate(IV) Salts of Univalent Cations. Spin Canting and Magnetic Ordering in K₂[ReI₆] withT_c= 24 K

Magnetic Studies on Hexaiodorhenate(IV) Salts of Univalent Cations. Spin Canting and Magnetic Ordering in K₂[ReI₆] withT_c= 24 K