Metathesis of a UV imido complex: a route to a terminal UV sulfide

The metathesis reaction of a U V imido complex supported by sterically demanding tris( tert -butoxy)siloxide ligands with CS 2 afforded a terminal U V thiocarbonate but metathesis with H 2 S afforded the first example of a terminal U V sulfide. Herein, we report the synthesis and characterisation of...

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Veröffentlicht in:Chemical science (Cambridge) 2017-08, Vol.8 (8), p.5319-5328
Hauptverfasser: Kelly, Rory P, Falcone, Marta, Lamsfus, Carlos Alvarez, Scopelliti, Rosario, Maron, Laurent, Meyer, Karsten, Mazzanti, Marinella
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container_issue 8
container_start_page 5319
container_title Chemical science (Cambridge)
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creator Kelly, Rory P
Falcone, Marta
Lamsfus, Carlos Alvarez
Scopelliti, Rosario
Maron, Laurent
Meyer, Karsten
Mazzanti, Marinella
description The metathesis reaction of a U V imido complex supported by sterically demanding tris( tert -butoxy)siloxide ligands with CS 2 afforded a terminal U V thiocarbonate but metathesis with H 2 S afforded the first example of a terminal U V sulfide. Herein, we report the synthesis and characterisation of the first terminal uranium( v ) sulfide and a related U V trithiocarbonate complex supported by sterically demanding tris( tert -butoxy)siloxide ligands. The reaction of the potassium-bound U V imido complex, [U(NAd){OSi(O t Bu) 3 } 4 K] ( 4 ), with CS 2 led to the isolation of perthiodicarbonate [K(18c6)] 2 [C 2 S 6 ] ( 6 ), with concomitant formation of the U IV complex, [U{OSi(O t Bu) 3 } 4 ], and S Created by potrace 1.16, written by Peter Selinger 2001-2019 C NAd. In contrast, the reaction of the U V imido complex, [K(2.2.2-cryptand)][U(NAd){OSi(O t Bu) 3 } 4 ] ( 5 ), with one or two equivalents of CS 2 afforded the trithiocarbonate complex, [K(2.2.2-cryptand)][U(CS 3 ){OSi(O t Bu) 3 } 4 ] ( 7 ), which was isolated in 57% yield, with concomitant elimination of the admantyl thiocyanate product, S C NAd. Complex 7 is likely formed by fast nucleophilic addition of a U V terminal sulfide intermediate, resulting from the slow metathesis reaction of the imido complex with CS 2 , to a second CS 2 molecule. The addition of a solution of H 2 S in thf (1.3 eq.) to 4 afforded the first isolable U V terminal sulfide complex, [K(2.2.2-cryptand)][US{OSi(O t Bu) 3 } 4 ] ( 8 ), in 41% yield. Based on DFT calculations, triple-bond character with a strong covalent interaction is suggested for the U–S bond in complex 7 .
doi_str_mv 10.1039/c7sc01111c
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Herein, we report the synthesis and characterisation of the first terminal uranium( v ) sulfide and a related U V trithiocarbonate complex supported by sterically demanding tris( tert -butoxy)siloxide ligands. The reaction of the potassium-bound U V imido complex, [U(NAd){OSi(O t Bu) 3 } 4 K] ( 4 ), with CS 2 led to the isolation of perthiodicarbonate [K(18c6)] 2 [C 2 S 6 ] ( 6 ), with concomitant formation of the U IV complex, [U{OSi(O t Bu) 3 } 4 ], and S Created by potrace 1.16, written by Peter Selinger 2001-2019 C NAd. In contrast, the reaction of the U V imido complex, [K(2.2.2-cryptand)][U(NAd){OSi(O t Bu) 3 } 4 ] ( 5 ), with one or two equivalents of CS 2 afforded the trithiocarbonate complex, [K(2.2.2-cryptand)][U(CS 3 ){OSi(O t Bu) 3 } 4 ] ( 7 ), which was isolated in 57% yield, with concomitant elimination of the admantyl thiocyanate product, S C NAd. Complex 7 is likely formed by fast nucleophilic addition of a U V terminal sulfide intermediate, resulting from the slow metathesis reaction of the imido complex with CS 2 , to a second CS 2 molecule. The addition of a solution of H 2 S in thf (1.3 eq.) to 4 afforded the first isolable U V terminal sulfide complex, [K(2.2.2-cryptand)][US{OSi(O t Bu) 3 } 4 ] ( 8 ), in 41% yield. 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Herein, we report the synthesis and characterisation of the first terminal uranium( v ) sulfide and a related U V trithiocarbonate complex supported by sterically demanding tris( tert -butoxy)siloxide ligands. The reaction of the potassium-bound U V imido complex, [U(NAd){OSi(O t Bu) 3 } 4 K] ( 4 ), with CS 2 led to the isolation of perthiodicarbonate [K(18c6)] 2 [C 2 S 6 ] ( 6 ), with concomitant formation of the U IV complex, [U{OSi(O t Bu) 3 } 4 ], and S Created by potrace 1.16, written by Peter Selinger 2001-2019 C NAd. In contrast, the reaction of the U V imido complex, [K(2.2.2-cryptand)][U(NAd){OSi(O t Bu) 3 } 4 ] ( 5 ), with one or two equivalents of CS 2 afforded the trithiocarbonate complex, [K(2.2.2-cryptand)][U(CS 3 ){OSi(O t Bu) 3 } 4 ] ( 7 ), which was isolated in 57% yield, with concomitant elimination of the admantyl thiocyanate product, S C NAd. Complex 7 is likely formed by fast nucleophilic addition of a U V terminal sulfide intermediate, resulting from the slow metathesis reaction of the imido complex with CS 2 , to a second CS 2 molecule. The addition of a solution of H 2 S in thf (1.3 eq.) to 4 afforded the first isolable U V terminal sulfide complex, [K(2.2.2-cryptand)][US{OSi(O t Bu) 3 } 4 ] ( 8 ), in 41% yield. 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Herein, we report the synthesis and characterisation of the first terminal uranium( v ) sulfide and a related U V trithiocarbonate complex supported by sterically demanding tris( tert -butoxy)siloxide ligands. The reaction of the potassium-bound U V imido complex, [U(NAd){OSi(O t Bu) 3 } 4 K] ( 4 ), with CS 2 led to the isolation of perthiodicarbonate [K(18c6)] 2 [C 2 S 6 ] ( 6 ), with concomitant formation of the U IV complex, [U{OSi(O t Bu) 3 } 4 ], and S Created by potrace 1.16, written by Peter Selinger 2001-2019 C NAd. In contrast, the reaction of the U V imido complex, [K(2.2.2-cryptand)][U(NAd){OSi(O t Bu) 3 } 4 ] ( 5 ), with one or two equivalents of CS 2 afforded the trithiocarbonate complex, [K(2.2.2-cryptand)][U(CS 3 ){OSi(O t Bu) 3 } 4 ] ( 7 ), which was isolated in 57% yield, with concomitant elimination of the admantyl thiocyanate product, S C NAd. Complex 7 is likely formed by fast nucleophilic addition of a U V terminal sulfide intermediate, resulting from the slow metathesis reaction of the imido complex with CS 2 , to a second CS 2 molecule. The addition of a solution of H 2 S in thf (1.3 eq.) to 4 afforded the first isolable U V terminal sulfide complex, [K(2.2.2-cryptand)][US{OSi(O t Bu) 3 } 4 ] ( 8 ), in 41% yield. Based on DFT calculations, triple-bond character with a strong covalent interaction is suggested for the U–S bond in complex 7 .</abstract><pub>Royal Society of Chemistry</pub><pmid>28970911</pmid><doi>10.1039/c7sc01111c</doi><tpages>10</tpages><oa>free_for_read</oa></addata></record>
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title Metathesis of a UV imido complex: a route to a terminal UV sulfide
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