Publikation: Synthesis of the First Stable Palladium Allenylidene Complexes
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2009
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Organometallics. 2009, 28(1), pp. 348-354. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om800843e
Zusammenfassung
Oxidative addition of BrCCC(=O)NR2 to [Pd(PPh3)4] affords the trans-alkynylbromopalladium complexes trans-[Br(PPh3)2Pd−CCC(=O)NR2] (NR2 = NMe2 (2a), N(CH2)4) (2b)). Subsequent reaction of 2a,b with PiPr3 in excess gives trans-[Br(PiPr3)2Pd−CCC(=O)NR2] (5a,b). The analogous reaction of 2b with P(C6H4OMe-4)3 gives trans-[Br(P{C6H4OMe-4}3)2Pd−CCC(=O)NR2] (7b), and that of 2a with trifluoroacetate gives trans-[(F3CCOO)(PPh3)2Pd−CCC(=O)NMe2] (9a). Methylation of 2a,b, 7b, and 9a with either MeOTf or [Me3O]BF4 and ethylation of 2a,b with [Et3O]BF4 yield the first cationic allenylidene complexes of palladium, trans-[R*(PR′3)2Pd−CCC(OMe)NR2]+X− (R* = Br, CF3COO; R′ = Ph, C6H4OMe-4, iPr; X = OTf, BF4).
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Fachgebiet (DDC)
540 Chemie
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Allenylidene complexes, Palladium, Alkinyl complexes
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KESSLER, Florian, Normen SZESNI, Kaija PÕHAKO, Bernhard WEIBERT, Helmut FISCHER, 2009. Synthesis of the First Stable Palladium Allenylidene Complexes. In: Organometallics. 2009, 28(1), pp. 348-354. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om800843eBibTex
@article{Kessler2009Synth-9993,
year={2009},
doi={10.1021/om800843e},
title={Synthesis of the First Stable Palladium Allenylidene Complexes},
number={1},
volume={28},
issn={0276-7333},
journal={Organometallics},
pages={348--354},
author={Kessler, Florian and Szesni, Normen and Põhako, Kaija and Weibert, Bernhard and Fischer, Helmut}
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<dcterms:abstract xml:lang="eng">Oxidative addition of BrCCC(=O)NR2 to [Pd(PPh3)4] affords the trans-alkynylbromopalladium complexes trans-[Br(PPh3)2Pd−CCC(=O)NR2] (NR2 = NMe2 (2a), N(CH2)4) (2b)). Subsequent reaction of 2a,b with PiPr3 in excess gives trans-[Br(PiPr3)2Pd−CCC(=O)NR2] (5a,b). The analogous reaction of 2b with P(C6H4OMe-4)3 gives trans-[Br(P{C6H4OMe-4}3)2Pd−CCC(=O)NR2] (7b), and that of 2a with trifluoroacetate gives trans-[(F3CCOO)(PPh3)2Pd−CCC(=O)NMe2] (9a). Methylation of 2a,b, 7b, and 9a with either MeOTf or [Me3O]BF4 and ethylation of 2a,b with [Et3O]BF4 yield the first cationic allenylidene complexes of palladium, trans-[R*(PR′3)2Pd−CCC(OMe)NR2]+X− (R* = Br, CF3COO; R′ = Ph, C6H4OMe-4, iPr; X = OTf, BF4).</dcterms:abstract>
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