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• W2017866224 abstract "Ein- und zweizähnig koordinierte Phosphinothioformamid-Komplexe lassen sich durch photochemische Substitution der Metallhexacarbonyle M(CO)6 (M  Cr (a), Mo (b), W (c)) darstellen. Durch Dunkelreaktion der M(CO)5 · THF-Addukte mit sekundären Thioamiden entstehen die P-koordinierten Pentacarbonyl-Komplexe [(CO)5MPPh2C(S)NHR1] (R1  Ph (1a–c), Me (2a)). Die Tieftemperatur-Photoreaktion von M(CO)5 · THF mit sekundären und tertiären Thioamiden führt zur Bildung der P, S-Chelatkomplexe . Die entsprechenden N-silylierten Komplexe 6a—c (R1 = Me3Si, R2 = Ph) erhält man durch direkte Photosubstitution von M(CO)6 in Cyclohexan-Lösung. Nach der gleichen Methode lassen sich die labilen Bis(thioformamid)-Komplexe [(CO)4M(PPh2C(S)NHMe)2] (7a–c, cis-trans-Isomere) in geringer Ausbeute darstellen. Während die Alkylierung der Chelatkomplexe 3a–c nicht gelingt, reagieren die sekundären Thioformamide mit n-BuLi/CH2Br2 quantitativ zu den Methylen-bis(thioformimidoestern) [Ph2PC(NR1)S]2CH2 (R1  Ph (8), Me (9)). Phosphine Substituted Chelate Ligands. XVIII. Penta- and Tetracarbonylmetal Complexes of Chromium, Molybdenum, and Tungsten with Secondary and Tertiary Phosphinothioformamide Ligands Mono- and bidentately coordinated phosphinothioformamide complexes are obtained by photochemical substitution of the metal hexacarbonyls M(CO)6 (M  Cr (a), Mo (b), W (c)). The M(CO)5 · THF adducts react with secondary thioamides under exclusion of light to give the P-coordinate pentacarbonyl complexes [(CO)5MPPh2C(S)NHR1] (R1  Ph (1a–c), Me (2a)). The photoreaction of M(CO)5 · THF with secondary and tertiary thioamides at low temperatures leads to the formation of the P, S-chelate complexes . The corresponding N-silylated complexes 6a–c (R1  Me3Si, R2  Ph) are obtained by direct photosubstitution of M(CO)6 in cyclohexane solution. The labile bis(thioformamide) complexes [(CO)4M(PPh2C(S)NHMe)2] (7a–c, cis-trans isomers) are synthesized in low yields according to the same procedure. The attempted alkylation of the chelate complexes 3a–c remains unsuccessful, whereas the secondary thioformamides react with n-BuLi/CH2Br2 to give the methylene bis(thioformirnidoesters) [Ph2PC(NR1)S]2CH2 (R1  Ph (8), Me (9)) in quantitative yields." @default.
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• W2017866224 date "1986-01-01" @default.
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• W2017866224 title "Phosphinsubstituierte Chelatliganden. XVIII. Penta- und Tetracarbonylmetall-Komplexe des Chroms, Molybd�ns und Wolframs mit sekund�ren und terti�ren Phosphinothioformamid-Liganden" @default.
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• W2017866224 doi "https://doi.org/10.1002/zaac.19865320116" @default.
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