Monomere und dimere Oxovanadium(IV)-phenolate: Synthese, Struktur und Reaktionen mit reduzierenden und arylierenden Reagenzien
✍ Scribed by K. Thiele; H. Görls; W. Imhof; W. Seidel
- Book ID
- 101298412
- Publisher
- John Wiley and Sons
- Year
- 1999
- Tongue
- German
- Weight
- 162 KB
- Volume
- 625
- Category
- Article
- ISSN
- 0372-7874
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✦ Synopsis
Inhaltsu È bersicht. Die Reaktion von [OVCl 2 (THF) 2 ] mit LiOMes ergibt dimeres [Li(Et 2 O) 2 OVCl 2 (l-OMes)] 2 (1), das mit weiterem LiOMes zum Substitutionsprodukt [Li(THF) 2 OV(OMes) 3 (THF)] (2) umgesetzt werden kann. Die Umsetzung von 1 mit LiMes liefert [Li(THF) 3 OVMes 3 ] (3) und [Li(THF) 3 OVMes 2 (OMes)] (4). Als Nebenprodukt einer ungekla È rten Reaktion zwischen [OV(OMes) 3 ] und Lithium wurde die Verbindung [{Li(THF) 2 OV(OMes) 2 (l-OH)} 2 ´2 THF] (6) isoliert. Die Strukturen von 1, 2, 3 und 6 wurden durch Kristallstrukturanalyse bestimmt. In 1 (monoklin, P2 1 /c, a = 9.522(1) A Ê , b = 19.777(2) A Ê , c = 12.311(1) A Ê , b = 104.45(1)°, Z = 2) liegen die Vanadiumatome quadratisch-pyramidal koordiniert vor und werden durch Phenolat-Liganden verbru È ckt. Das Zentralatom in 2 (monoklin, P2 1 /c, a = 17,755(2) A Ê , b = 11,629(1) A Ê , c = 20,956(3) A Ê , b = 113,98(1)°, Z = 4) hat trigonal-bipyramidale Koordination, die durch Anlagerung eines THF-Donors erreicht wird. Die (THF) 2 Li-Einheit ist u È ber Phenolat-Bru È kken gebunden. In der Struktur von 3 (orthorhombisch, P2 1 2 1 2 1 , a = 15,465(2) A Ê , b = 15,456(2) A Ê , c = 15,469(2) A Ê , Z = 4) liegen zwei u È ber das Oxo-Sauerstoffatom verbundene Tetraeder vor. Dimeres 6 (triklin, P1, a = 10,780(4) A Ê , b = 11,428(2) A Ê , c = 13,734(3) A Ê , a = 77,24(2)°, b = 84,79(2)°, c = 74,35(2)°, Z = 1) a È hnelt in seinem Aufbau 1, wobei die beiden Vanadiumatome u È ber zwei OH-Gruppen und die Li-Kationen u È ber Phenolat-Liganden mit den V-Atomen verbru È ckt sind. Monomeric and Dimeric Oxovanadium(IV)-phenolate Complexes: Synthesis, Structure, and Reaction with a Reducing and Arylation Agent Abstract. Reaction of [OVCl 2 (THF) 2 ] with LiOMes yields dimeric [Li(Et 2 O) 2 OVCl 2 (l-OMes)] 2 (1) which can be converted with excess LiOMes to the substitution product [Li(THF) 2 OV(OMes) 3 (THF)] (2). Treatment of (1) with LiMes results in the formation of complexes [Li(THF) 3 OVMes 3 ] (3) and [Li(THF) 3 OVMes 2 (OMes)] (4). Complex [{Li(THF) 2 OV(OMes) 2 (l-OH)} 2 ´2 THF] (6) has been isolated as a by-product of an unknown reaction of [OV(OMes) 3 ] and Li. The structures of 1, 2, 3, and 6 have been determined by X-ray analysis. In 1 (monoclinic, P2 1 /c, a = 9.522(1) A Ê , b = 19.777(2) A Ê , c = 12.311(1) A Ê , b = 104.45(1)°, Z = 2) the vanadium atoms which are bridged by the phenolate ligands show a square-pyramidal coordination sphere. The central atom in 2 (monoclinic, P2 1 /c, a = 17.755(2) A Ê , b = 11.629(1) A Ê , c = 20.956(3) A Ê , b = 113.98(1)°, Z = 4) has a bipyramidal environment which is realized by coordination of a THF donor molecule. The (THF) 2 Li fragment is bound via bridging phenolate ligands. The structure of 3 (orthorhombic, P2 1 2 1 2 1 , a = 15.465(2) A Ê , b = 15.456(2) A Ê , c = 15.469(2) A Ê , Z = 4) is built up by two tetrahedrons linked by the oxo atom. Dimeric 6 (triclinic, P1, a = 10.780(4) A Ê , b = 11.428(2) A Ê , c = 13.734(3) A Ê , a = 77.24(2)°, b = 84.79(2)°, c = 74.35(2)°, Z = 1) has a structure similar to 1. The vanadium atoms are bridged by two OH groups while phenolate ligands link the lithium cations with the vanadium atoms.