The monomeric pentacyanocobaltate(II) anion: Preparation and properties of thallium(I) pentacyanocobaltate(II)

Mosha, Dms

doi:10.1021/ed059p1057

Cited by 1 publication

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References 8 publications

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“…In the group 15 family, phosphorus is more similar to its diagonal relative, carbon, than to nitrogen [ 42 ]. Thallium is also known to be monovalent and has an ionic radius that is similar to that of potassium, so it is often presumed to be a pseudo alkali metal [ 43 ]. The isolation and characterization of the singly bonded organothallium phosphorus molecule, (Me 3 SiCH 2 ) 3 Tl⎼P(SiMe 3 ) 3 , was experimentally reported about twenty years ago [ 44 ].…”

Section: Introductionmentioning

confidence: 99%

Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study

Mei

2017

Molecules

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Three computational methods (M06-2X/Def2-TZVP, B3PW91/Def2-TZVP and B3LYP/LANL2DZ+dp) were used to study the effect of substitution on the potential energy surfaces of RTl≡PR (R = F, OH, H, CH3, SiH3, SiMe(SitBu3)2, SiiPrDis2, Tbt (=C6H2-2,4,6-(CH(SiMe3)2)3), and Ar* (=C6H3-2,6-(C6H2-2, 4,6-i-Pr3)2)). The theoretical results show that these triply bonded RTl≡PR compounds have a preference for a bent geometry (i.e., ∠R⎼Tl⎼P ≈ 180° and ∠Tl⎼P⎼R ≈ 120°). Two valence bond models are used to interpret the bonding character of the Tl≡P triple bond. One is model [I], which is best described as TlP. This interprets the bonding conditions for RTl≡PR molecules that feature small ligands. The other is model [II], which is best represented as TlP. This explains the bonding character of RTl≡PR molecules that feature large substituents. Irrespective of the types of substituents used for the RTl≡PR species, the theoretical investigations (based on the natural bond orbital, the natural resonance theory, and the charge decomposition analysis) demonstrate that their Tl≡P triple bonds are very weak. However, the theoretical results predict that only bulkier substituents greatly stabilize the triply bonded RTl≡PR species, from the kinetic viewpoint.

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Section: Introductionmentioning

confidence: 99%

Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study

Mei

2017

Molecules

View full text Add to dashboard Cite

show abstract

The monomeric pentacyanocobaltate(II) anion: Preparation and properties of thallium(I) pentacyanocobaltate(II)

Cited by 1 publication

References 8 publications

Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study

Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study

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