The Chemistry of the Cluster Compounds of Technetium

Spitsyn, V.I.; Kuzina, A.F.; Oblova, A. A.; Kryuchkov, S. V.

doi:10.1070/rc1985v054n04abeh003050

Cited by 18 publications

(8 citation statements)

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“…As could be expected from Fig. 4, one unpaired electron is shared by two Tc atoms that form an M7M bond of high order (the Tc7Tc distances in d 4 ± d 5 complexes lie within the limits 2.10 ± 2.15 # A) 1,2,51 in the molecules of these compounds. It has been shown 3, 9, 52 ± 54 5 and 6, respectively.…”

Section: Magnetochemistry Of Technetium Oxo and Halide Complexessupporting

confidence: 77%

“…4) are characteristic of these compounds. 1,2,51 These complexes have an eclipsed conformation of ligands (the idealised D 4h symmetry, see Fig. 1 a,b) and Tc7Tc distances in the range from 2.16 to 2.19 # A.…”

Section: Magnetochemistry Of Technetium Oxo and Halide Complexesmentioning

confidence: 97%

“…In these complexes, the M7M interactions result in appreciable shortening of the Tc7Tc distances compared to analogous distances in compact metallic Tc. 1,2,51 The compounds studied 2, 51 can be divided into two structural types, viz., dinuclear complexes (clusters) with multiple M7M bonds and polynuclear clusters.…”

Section: Magnetochemistry Of Technetium Oxo and Halide Complexesmentioning

confidence: 99%

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Physicochemical properties of technetium acido clusters

Kryutchkov¹

1998

Russ. Chem. Rev.

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The review is concerned with the electronic and molec ular structure and physicochemical properties of all types of technetium clusters with acido ligands described to date. As a typical cluster-forming metal, technetium possesses a number of specific, anomalous cluster-forming properties that can be interpreted in terms of greater capability of outer diffuse 5s(5p) AOs to participate in the formation of additional M7M bonds in technetium acido clusters as compared to analogous clusters of other transition d-elements. Theoretical interpretation of the electronic and molecular structure and properties of technetium clusters has been confirmed by experimental data (X-ray analysis, magnetochemistry, and EPR, optical, X-ray photoelectron and X-ray emission spectroscopy). The experimentally observed increased stability of technetium clusters with odd numbers of `metallic' electrons and a decrease in the effective charge on Tc atoms upon formation of the M7M bonds are discussed. Recently found `anomalous' properties of technetium and rhenium compounds with ferrocenium cations (in particular, unusual low-temperature electron emission on X-ray irradiation) are also considered. The bibliography includes 101 references.

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Section: Magnetochemistry Of Technetium Oxo and Halide Complexessupporting

confidence: 77%

Section: Magnetochemistry Of Technetium Oxo and Halide Complexesmentioning

confidence: 97%

Section: Magnetochemistry Of Technetium Oxo and Halide Complexesmentioning

confidence: 99%

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Physicochemical properties of technetium acido clusters

Kryutchkov¹

1998

Russ. Chem. Rev.

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“…TcN was reported to be NaCl type. [20] As for manganese nitrides, ε-Mn 4 N, [21] ζ -Mn 2 N, [22] η-Mn 3 N 2 , [23][24][25] θ-Mn 6 N 5 , [23,24] and Mn 2 N 0.86 [26] were synthesized under pressures no more than 1 GPa and high temperatures ranging from 400 to 700…”

Section: Introductionmentioning

confidence: 99%

The effect of structure and phase transformation on the mechanical properties of Re₂N and the stability of Mn₂N

Wang

2011

J Comput Chem

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First-principles calculations were carried out on recently synthesized Re₂N and Re₃N as well as hypothetical Tc and Mn nitrides. It is found that structure and covalent bonds play an important role in determining mechanical properties. Under a large strain along (0001)<1010> direction, Re₂N undergoes a phase transformation with a slight increase in ideal shear strength. On the other hand, it is transformed into a phase with weaker mechanical properties, if the strain is along Re₂ <1210> direction. Mn₂N can be synthesized under moderate conditions due to its more negative formation energy. Re₂N, Re₃N, and Mn₂ N show structure-related mechanical property under larger strains to ReB₂ but exhibit much lower ideal strengths, which is attributed to the larger ionicity of cation-anion bond. Three-dimensional framework of strong covalent bonds is thus highly recommended to design superhard materials.

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“…Many of the complexes depicted in Scheme 3 and described in the final paragraph of the preceding section, (10)- (12), should also be mentioned here since they contain nitrogen and phosphorus donor ligands. 57 " 61 The photolytic and thermal substitution reactions of [Tc 2 (CO) 1 0 ] (1) with PF 3 were studied.…”

Section: Nitrogen and Phosphorusmentioning

confidence: 98%