Cs<sub>2</sub>Pt: A Platinide(‐<scp>II</scp>) Exhibiting Complete Charge Separation

Karpov, Andrey; Nuß, Jürgen; Wedig, Ulrich; Jansen, Martin

doi:10.1002/anie.200352314

Cited by 100 publications

(85 citation statements)

References 37 publications

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“…7, both are metallic. While weakly metallic Rb 3 AuO extrapolates to the same OS as Cs 3 The example of an unexpected bonding pattern concerns two platinides: red transparent Cs 2 Pt [194] and black BaPt [195]. In line with the 12−N rule, Cs 2 Pt contains isolated Pt 2− anions, a relativistic sulfide.…”

Section: What If the Structure Becomes Metallic?mentioning

confidence: 81%

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Karen

McArdle

Takats

2014

Pure and Applied Chemistry

111

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A generic definition of oxidation state (OS) is formulated: "The OS of a bonded atom equals its charge after ionic approximation". In the ionic approximation, the atom that contributes more to the bonding molecular orbital (MO) becomes negative. This sign can also be estimated by comparing Allen electronegativities of the two bonded atoms, but this simplification carries an exception when the more electronegative atom is bonded as a Lewis acid. Two principal algorithms are outlined for OS determination of an atom in a compound; one based on composition, the other on topology. Both provide the same generic OS because both the ionic approximation and structural formula obey rules of stable electron configurations. A sufficiently simple empirical formula yields OS via the algorithm of direct ionic approximation (DIA) by these rules. The topological algorithm works on a Lewis formula (for a molecule) or a bond graph (for an extended solid) and has two variants. One assigns bonding electrons to more electronegative bond partners, the other sums an atom's formal charge with bond orders (or bond valences) of sign defined by the ionic approximation of each particular bond at the atom. A glossary of terms and auxiliary rules needed for determination of OS are provided, illustrated with examples, and the origins of ambiguous OS values are pointed out. An electrochemical OS is suggested with a nominal value equal to the average OS for atoms of the same element in a moiety that is charged or otherwise electrochemically relevant.

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Section: What If the Structure Becomes Metallic?mentioning

confidence: 81%

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Karen

McArdle

Takats

2014

Pure and Applied Chemistry

111

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“…The XeAu 2 and XePt are two particularly reasonable stoichiometries, which contain Au 21 and isoelectronic Pt 22 , as far as ionic formulation is enforced. 124 Such stoichiometries (i) favour natural Xe d+ TM s2 polarization and (ii) utilize the enhanced electron-accepting abilities of the relativistic 6s orbitals of Au and Pt.…”

Section: Metallic Alloys Of Xementioning

confidence: 99%

Atypical Compounds of Gases, which Have Been Called “Noble”

Grochala

2007

ChemInform

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“…According to the Pauling scale, the values are as follows: χ(Y) = 1.22, χ(Dy) = 1.22, χ(Ho) = 1.23, χ(Er) = 1.24, χ(Tm) = 1.25, χ(Pt) = 2.28, and χ(Al) = 1.61 [30]. Because all reported compounds are of a metallic nature, a distinct ionic platinide character as found in A 2 Pt (A = K [43], Rb [43], Cs [43,44]) is highly unlikely, especially when considering the three-dimensional framework with strong covalent bonding character formed by Pt and Al. Therefore, XPS measurements were performed to investigate exemplarily the platinide character of YPt 2 Al 3 along with the reference substances YPt 5 Al 2 (anti-ZrNi 2 Al 5 -type [45]), YPtAl (TiNiSi-type [31]), and elemental Pt.…”

Section: X-ray Photoelectron Spectroscopymentioning

confidence: 88%

Crystal Structure, Spectroscopic Investigations, and Physical Properties of the Ternary Intermetallic REPt2Al3 (RE = Y, Dy–Tm) and RE2Pt3Al4 Representatives (RE = Tm, Lu)

et al. 2018

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Abstract:The REPt 2 Al 3 compounds of the late rare-earth metals (RE = Y, Dy-Tm) were found to crystallize isostructural. Single-crystal X-ray investigations of YPt 2 Al 3 revealed an orthorhombic unit cell (a = 1080.73(6), b = 1871.96(9), c = 413.04(2) pm, wR2 = 0.0780, 942 F 2 values, 46 variables) with space group Cmmm (oC48; q 2 pji 2 hedb). A comparison with the Pearson database indicated that YPt 2 Al 3 forms a new structure type, in which the Pt and Al atoms form a [Pt 2 Al 3 ] δ− polyanion and the Y atoms reside in the cavities within the framework. Via a group-subgroup scheme, the relationship between the PrNi 2 Al 3 -type structure and the new YPt 2 Al 3 -type structure was illustrated. The compounds with RE = Dy-Tm were characterized by powder X-ray diffraction experiments. While YPt 2 Al 3 is a Pauli-paramagnet, the other REPt 2 Al 3 (RE = Dy-Tm) compounds exhibit paramagnetic behavior, which is in line with the rare-earth atoms being in the trivalent oxidation state. DyPt 2 Al 3 and TmPt 2 Al 3 exhibit ferromagnetic ordering at T C = 10.8(1) and 4.7(1) K and HoPt 2 Al 3 antiferromagnetic ordering at T N = 5.5(1) K, respectively. Attempts to synthesize the isostructural lutetium compound resulted in the formation of Lu 2 Pt 3 Al 4 (Ce 2 Ir 3 Sb 4 -type, Pnma, a = 1343.4(2), b = 416.41(8), c = 1141.1(2) pm), which could also be realized with thulium. The structure was refined from single-crystal data (wR2 = 0.0940, 1605 F 2 values, 56 variables). Again, a polyanion with bonding Pt-Al interactions was found, and the two distinct Lu atoms were residing in the cavities of the [Pt 3 Al 4 ] δ-framework. X-ray photoelectron spectroscopy (XPS) measurements were conducted to examine the electron transfer from the rare-earth atoms onto the polyanionic framework.

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Cs₂Pt: A Platinide(‐II) Exhibiting Complete Charge Separation

Cited by 100 publications

References 37 publications

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Atypical Compounds of Gases, which Have Been Called “Noble”

Crystal Structure, Spectroscopic Investigations, and Physical Properties of the Ternary Intermetallic REPt2Al3 (RE = Y, Dy–Tm) and RE2Pt3Al4 Representatives (RE = Tm, Lu)

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Cs2Pt: A Platinide(‐II) Exhibiting Complete Charge Separation

Cited by 100 publications

References 37 publications

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Atypical Compounds of Gases, which Have Been Called “Noble”

Crystal Structure, Spectroscopic Investigations, and Physical Properties of the Ternary Intermetallic REPt2Al3 (RE = Y, Dy–Tm) and RE2Pt3Al4 Representatives (RE = Tm, Lu)

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Cs₂Pt: A Platinide(‐II) Exhibiting Complete Charge Separation