Coordination chemistry of the cyclo-(P(5)tBu(4))(-) ion: monomeric and oligomeric copper(I), silver(I) and gold(I) complexes
| Autor: | Henry Bittig, Santiago Gómez-Ruiz, Sebastian Bauer, Peter Lönnecke, Andrea Schisler, Robert Wolf, Evamarie Hey-Hawkins |
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| Rok vydání: | 2008 |
| Předmět: |
Models
Molecular Magnetic Resonance Spectroscopy Silver Stereochemistry chemistry.chemical_element Stereoisomerism Crystal structure Crystallography X-Ray Medicinal chemistry Catalysis Coordination complex Adduct Heterocyclic Compounds 1-Ring Organophosphorus Compounds Organometallic Compounds Molecule Group 2 organometallic chemistry chemistry.chemical_classification Ions Molecular Structure Organic Chemistry General Chemistry Nuclear magnetic resonance spectroscopy Copper chemistry Gold |
| Zdroj: | Chemistry (Weinheim an der Bergstrasse, Germany). 14(15) |
| ISSN: | 0947-6539 |
| Popis: | [Na{cyclo-(P(5)tBu(4))}] (1) reacts with [CuCl(PCyp(3))(2)] (Cyp=cyclo-C(5)H(9)) and [CuCl(PPh(3))(3)] (1:1) to give the corresponding copper(I) complexes with a tetra-tert-butylcyclopentaphosphanide ligand, [Cu{cyclo- (P(5)tBu(4))}(PCyp(3))(2)] (2) and [Cu{cyclo-(P(5)tBu(4))}(PPh(3))(2)] (3). The CuCl adduct of 2, [Cu(2)(mu-Cl){cyclo-(P(5)tBu(4))}(PCyp(3))(2)] (4), was obtained from the reaction of 1 with [CuCl(PCyp(3))(2)] (1:2). Compounds 2 and 3 rearrange, even at -27 degrees C, to give [Cu(4){cyclo- (P(4)tBu(3))PtBu}(4)] (5), in which ring contraction of the [cyclo-(P(5)tBu(4))](-) anion has occurred. The reaction of 1 with [AgCl(PCyp(3))](4) or [AgCl(PPh(3))(2)] (1:1) leads to the formation of [Ag(4){cyclo-(P(4)tBu(3))PtBu}(4)] (6). Intermediates, which are most probably mononuclear, "[Ag{cyclo-(P(5)tBu(4))}(PR(3))(2)]" (R=Cyp, Ph) could be detected in the reaction mixtures, but not isolated. Finally, the reaction of 1 with [AuCl(PCyp(3))] (1:1) yielded [Au{cyclo-(P(5)tBu(4))}(PCyp(3))] (7), whereas an inseparable mixture of [Au(3){cyclo-(P(5)tBu(4))}(3)] (8) and [Au(4){cyclo-(P(4)tBu(3))PtBu}(4)] (9) was obtained from the analogous reaction with [AuCl(PPh(3))]. Complexes 3-7 were characterised by (31)P NMR spectroscopy, and X-ray crystal structures were determined for 3-9. |
| Databáze: | OpenAIRE |
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