| Autor: |
Eberle L; Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 276, D-69120 Heidelberg, Germany., Kreis F; Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 276, D-69120 Heidelberg, Germany., Stein CAM; Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 276, D-69120 Heidelberg, Germany., Mörsdorf JM; Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 276, D-69120 Heidelberg, Germany., Ballmann J; Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 276, D-69120 Heidelberg, Germany. |
| Jazyk: |
angličtina |
| Zdroj: |
Inorganic chemistry [Inorg Chem] 2023 Jun 05; Vol. 62 (22), pp. 8635-8646. Date of Electronic Publication: 2023 May 19. |
| DOI: |
10.1021/acs.inorgchem.3c00769 |
| Abstrakt: |
An [AsCCAs] ligand featuring a central alkyne and two flanking arsenic donors was employed for the synthesis of a trihydrido rhenium complex, while the corresponding phosphorus ligand was shown to be less suited. The reactivity of the former trihydride [AsCCAs]ReH 3 ( 3 ) was examined in detail, which revealed that two alternative reaction channels may be entered in dependence of the substrate. Upon reaction of 3 with PhC≡CPh, ethylene, and CS 2 , monohydrides of the general formula [AsCCAs]Re(L)H with L = η 2 -PhC≡CPh ( 4 ), η 2 -H 2 C═CH 2 ( 5 ), and η 2 -CS 2 ( 6 ) were formed along with H 2 . In contrast, insertion products of the type [AsCCAs]Re(X)H 2 ( 7 -9) were obtained upon treatment of 3 with CyN═C═NCy, PhN═C═O, and Ph 2 C═C═O, while CO 2 failed to react with 3 under identical reaction conditions. Given that several productive reactions between CO 2 and hydrido rhenium carbonyls have been reported in the literature, 3 was further derivatized by introducing CO and t BuNC coligands, respectively. This led to the isolation of trans -[AsCCAs]ReH(CO) 2 ( trans - 10 ) and trans -[AsCCAs]ReH(CN t Bu) 2 ( trans - 11 ), which were shown to thermally isomerize to the corresponding cis -configured products, cis - 10 and cis - 11 . Interestingly, only the cis -complexes were found to react with CO 2 , which was rationalized by evaluating the relative nucleophilicities of the hydrides in cis - 10 , trans - 10 , cis - 11 , and trans - 11 via Fukui analysis. The formates cis -[AsCCAs]Re(OCHO)(CO) 2 ( 12 ) and cis -[AsCCAs]Re(OCHO)(CN t Bu) 2 ( 13 ) were isolated and shown to contain κ 1 - O -coordinated formate moieties. Treatment of 12 with [LutH]Cl/B(C 6 F 5 ) 3 (or with Ph 3 SiCl) led to the liberation of [LutH][OCHO···B(C 6 F 5 ) 3 ] (or triphenylsilyl formate) with concomitant formation of the expected chloro complex cis -[AsCCAs]ReCl(CO) 2 ( 14 ). In a closed synthetic cycle, hydride 12 was regenerated from the latter chloride using NaBEt 3 H as a hydride source. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
|
