Synthesis, Characterization, and Reactivity of Isocyanidephosphidoniobocene Derivatives: X-ray Diffraction Structures of New Isocyanideniobocene Complexes, [Nb(
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- 作者：Antonio Antiñ ; olo ; David Evrard ; Santiago Garcí ; a-Yuste ; Antonio Otero ; Juan C. Pé ; rez-Flores ; Rebeca Reguillo-Carmona ; Ana M. Rodrí ; guez ; and Elena Villaseñ ; or
- 刊名：Organometallics
- 出版年：2006
- 出版时间：July 17, 2006
- 年：2006
- 卷：25
- 期：15
- 页码：3670 - 3677
- 全文大小：170K
- 年卷期：v.25,no.15(July 17, 2006)
- ISSN：1520-6041
文摘
The reaction of the hydride niobocene complexes [Nb(
5-C5H4SiMe3)2H(L)] [L = CNBun (1), CNCy(2), and CNXylyl (3)] with ClPPh2 yielded the cationic niobocene complexes [Nb(5-C5H4SiMe3)2(PHPh2)(L)]Cl [L = CNBun (4), CNCy (5), and CNXylyl (6)]. Treatment of these complexes with NaOH yieldeda new family of phosphidoniobocene derivatives [Nb(5-C5H4SiMe3)2(PPh2)(L)] [L = CNBun (7), CNCy(8), and CNXylyl (9)] by elimination of the hydrogen atom directly bonded to the phosphorus. Thecationic d2 species [Nb(5-C5H4SiMe3)2(PRPh2)(L)]X [R = Me, X = I, L = CNBun (10), CNCy (11),and CNXylyl (12); R = CH2Ph, X = Br, CNBun (13), CNCy (14), and CNXylyl (15); R = CH2CH2Ph,X = Br, CNBun (16), CNCy (17), and CNXylyl (18)] were prepared by the reaction of alkyl halidesRX (R = Me, X = I; CH2Ph, X = Br; CH2CH2Ph, X = Br) with 7, 8, or 9 by electrophilic attack onthe phosphorus atom present in the phosphido terminal ligand. In the same way, the reaction of 9 withICH2CH2I or iodine yielded the complex [Nb(5-C5H4SiMe3)2(P(I)Ph2)(CNXylyl)]I3 (19). The insertionreaction of carbon disulfide into the Nb-P bond of 7, 8, or 9 yielded a new family of diphenylphosphidodithioformato complexes with the niobocene system [Nb(5-C5H4SiMe3)2(
1-S-SC(S)(PPh2))(L)][L = CNBun (20), CNCy (21), and CNXylyl (22)]. The molecular structures of 11 and 12 were determinedby single-crystal X-ray diffraction studies.
5-C5H4SiMe3)2H(L)] [L = CNBun (1), CNCy(2), and CNXylyl (3)] with ClPPh2 yielded the cationic niobocene complexes [Nb(5-C5H4SiMe3)2(PHPh2)(L)]Cl [L = CNBun (4), CNCy (5), and CNXylyl (6)]. Treatment of these complexes with NaOH yieldeda new family of phosphidoniobocene derivatives [Nb(5-C5H4SiMe3)2(PPh2)(L)] [L = CNBun (7), CNCy(8), and CNXylyl (9)] by elimination of the hydrogen atom directly bonded to the phosphorus. Thecationic d2 species [Nb(5-C5H4SiMe3)2(PRPh2)(L)]X [R = Me, X = I, L = CNBun (10), CNCy (11),and CNXylyl (12); R = CH2Ph, X = Br, CNBun (13), CNCy (14), and CNXylyl (15); R = CH2CH2Ph,X = Br, CNBun (16), CNCy (17), and CNXylyl (18)] were prepared by the reaction of alkyl halidesRX (R = Me, X = I; CH2Ph, X = Br; CH2CH2Ph, X = Br) with 7, 8, or 9 by electrophilic attack onthe phosphorus atom present in the phosphido terminal ligand. In the same way, the reaction of 9 withICH2CH2I or iodine yielded the complex [Nb(5-C5H4SiMe3)2(P(I)Ph2)(CNXylyl)]I3 (19). The insertionreaction of carbon disulfide into the Nb-P bond of 7, 8, or 9 yielded a new family of diphenylphosphidodithioformato complexes with the niobocene system [Nb(5-C5H4SiMe3)2(1-S-SC(S)(PPh2))(L)][L = CNBun (20), CNCy (21), and CNXylyl (22)]. The molecular structures of 11 and 12 were determinedby single-crystal X-ray diffraction studies.