Unknown

Dataset Information

0

Uranium versus Thorium: Synthesis and Reactivity of [η5 -1,2,4-(Me3 C)3 C5 H2 ]2 U[η2 -C2 Ph2 ].

ABSTRACT: The synthesis, electronic structure, and reactivity of a uranium metallacyclopropene were comprehensively studied. Addition of diphenylacetylene (PhC≡CPh) to the uranium phosphinidene metallocene [η5 -1,2,4-(Me3 C)3 C5 H2 ]2 U=P-2,4,6-tBu3 C6 H2 (1) yields the stable uranium metallacyclopropene, [η5 -1,2,4-(Me3 C)3 C5 H2 ]2 U[η2 -C2 Ph2 ] (2). Based on density functional theory (DFT) results the 5f orbital contributions to the bonding within the metallacyclopropene U-(η2 -C=C) moiety increases significantly compared to the related ThIV compound [η5 -1,2,4-(Me3 C)3 C5 H2 ]2 Th[η2 -C2 Ph2 ], which also results in more covalent bonds between the [η5 -1,2,4-(Me3 C)3 C5 H2 ]2 U2+ and [η2 -C2 Ph2 ]2- fragments. Although the thorium and uranium complexes are structurally closely related, different reaction patterns are therefore observed. For example, 2 reacts as a masked synthon for the low-valent uranium(II) metallocene [η5 -1,2,4-(Me3 C)3 C5 H2 ]2 UII when reacted with Ph2 E2 (E=S, Se), alkynes and a variety of hetero-unsaturated molecules such as imines, ketazine, bipy, nitriles, organic azides, and azo derivatives. In contrast, five-membered metallaheterocycles are accessible when 2 is treated with isothiocyanate, aldehydes, and ketones.

SUBMITTER: Wang D 

PROVIDER: S-EPMC8251885 | biostudies-literature | 2021 Apr

REPOSITORIES: biostudies-literature

Json Xml
altmetric image

Publications

Uranium versus Thorium: Synthesis and Reactivity of [η<sup>5</sup> -1,2,4-(Me<sub>3</sub> C)<sub>3</sub> C<sub>5</sub> H<sub>2</sub> ]<sub>2</sub> U[η<sup>2</sup> -C<sub>2</sub> Ph<sub>2</sub> ].

Wang Deqiang D   Ding Wanjian W   Hou Guohua G   Zi Guofu G   Walter Marc D MD  

Chemistry (Weinheim an der Bergstrasse, Germany) 20210316 22

The synthesis, electronic structure, and reactivity of a uranium metallacyclopropene were comprehensively studied. Addition of diphenylacetylene (PhC≡CPh) to the uranium phosphinidene metallocene [η<sup>5</sup> -1,2,4-(Me<sub>3</sub> C)<sub>3</sub> C<sub>5</sub> H<sub>2</sub> ]<sub>2</sub> U=P-2,4,6-tBu<sub>3</sub> C<sub>6</sub> H<sub>2</sub> (1) yields the stable uranium metallacyclopropene, [η<sup>5</sup> -1,2,4-(Me<sub>3</sub> C)<sub>3</sub> C<sub>5</sub> H<sub>2</sub> ]<sub>2</sub> U[η<sup>2  ...[more]

Similar Datasets

Unknown Influence of 1,2,4-Tri-&lt;i&gt;tert&lt;/i&gt;-butylcyclopentadienyl Ligand on the Reactivity of the Thorium Bipyridyl Metallocene [η&lt;sup&gt;5&lt;/sup&gt;-1,2,4-(Me&lt;sub&gt;3&lt;/sub&gt;C)&lt;sub&gt;3&lt;/sub&gt;C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;2&lt;/sub&gt;]&lt;sub&gt;2&lt;/sub&gt;Th(bipy)].
| S-EPMC11483809 | biostudies-literature
Unknown Synthesis, structures and magnetic properties of [(η<sup>9</sup>-C<sub>9</sub>H<sub>9</sub>)Ln(η<sup>8</sup>-C<sub>8</sub>H<sub>8</sub>)] super sandwich complexes.
| S-EPMC6637141 | biostudies-literature
Unknown A Neutral "Aluminocene" Sandwich Complex: η<sup>1</sup> - versus η<sup>5</sup> -Coordination Modes of a Pentaarylborole with ECp* (E=Al, Ga; Cp*=C<sub>5</sub> Me<sub>5</sub> ).
| S-EPMC6856865 | biostudies-literature
Unknown Thorium- and uranium-azide reductions: a transient dithorium-nitride <i>versus</i> isolable diuranium-nitrides.
| S-EPMC6446963 | biostudies-literature
Unknown S<sub>N</sub>2 versus E2 Competition of F<sup>-</sup> and PH<sub>2</sub><sup>-</sup> Revisited.
| S-EPMC7656514 | biostudies-literature
Unknown Synthesis, structure, and reactivity of uranium(vi) nitrides.
| S-EPMC8208130 | biostudies-literature
Unknown Uranium and thorium complexes of the phosphaethynolate ion.
| S-EPMC6054101 | biostudies-literature
Unknown Crystal structure of the [(THF)Cs(μ-η<sup>5</sup>:η<sup>5</sup>-Cp')<sub>3</sub>Yb] <sub><i>n</i></sub> oligomer.
| S-EPMC7336790 | biostudies-literature
Unknown Reactivity of uranium(iii) with H<sub>2</sub>E (E = S, Se, Te): synthesis of a series of mononuclear and dinuclear uranium(iv) hydrochalcogenido complexes.
| S-EPMC5811169 | biostudies-literature
Unknown Mesoionic Carbene Complexes of Uranium(IV) and Thorium(IV).
| S-EPMC9490841 | biostudies-literature