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• W2060125504 abstract "The trihydride complex [Nb(η5-C5H4SiMe3)2(H)3] (1) reacts with diphenylphosphane to afford the monohydride [Nb(η5-C5H4SiMe3)2(H)(PHPh2)] (3). The synthesis of complex 3 has also been achieved from the initial formation of the phosphonium salt [Nb(η5-C5H4SiMe3)2(H)2(PHPh2)]Cl (2) by reaction of the trihydride complex [Nb(η5-C5H4SiMe3)2(H)3] (1) with chlorodiphenylphosphane, followed by deprotonation of this salt in aqueous NaOH. Protonation of complex 3 at low temperature with a slight excess of CF3COOH or CF3COOD leads to the η2-dihydrogen complex [Nb(η5-C5H4SiMe3)2(η2-H2)(PHPh2)]CF3CO2 (4) or its monodeuterated isotopomer [Nb(η5-C5H4SiMe3)2(η2-HD)(PHPh2)]CF3CO2 (5). When the temperature is increased to room temperature, complexes 4 and 5 transform into the transoid dihydrides [Nb(η5-C5H4SiMe3)2(H)2(PHPh2)]CF3CO2 (6) and [Nb(η5-C5H4SiMe3)2(H)2(PDPh2)]CF3CO2 (7), respectively. Complex 3 undergoes an insertion of CS2 into the niobium−hydrogen bond to give the η1-dithioformato complex [Nb(η5-C5H4SiMe3)2(PHPh2)(η1-S-S(S)CH)] (8). This complex could be detected by NMR spectroscopy but could not be isolated due to rapid conversion into the η2-dithioformato complex [Nb(η5-C5H4SiMe3)2(η2-S,S-SSCH)] (9) by loss of the phosphane molecule. Complex 3 also reacts with CO2 to give the η2-formato complex [Nb(η5-C5H4SiMe3)2(η2-O,O-OOCH)] (10); in this case the η1-formato complex could not be detected. The reagent ClPPh2 very smoothly inserts into the Nb−H bond of the complexes [Nb(η5-C5H4SiMe3)2(H)(L)] [L = PHPh2, CN(xylyl), CO; xylyl = 2,6-dimethylphenyl], yielding the new ionic complexes [Nb(η5-C5H4SiMe3)2(PHPh2)(L)]Cl [L = PHPh2 (11), CN(xylyl) (12), CO (13)]. All the complexes described have been characterized by analytical and spectroscopic methods." @default.
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• W2060125504 date "2000-07-01" @default.
• W2060125504 modified "2023-10-17" @default.
• W2060125504 title "New Studies on the Reactivity of Hydride-Containing Niobocene Complexes Towards Insertion and Protonation Processes" @default.
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• W2060125504 doi "https://doi.org/10.1002/1099-0682(200007)2000:7<1437::aid-ejic1437>3.0.co;2-j" @default.
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