Coordination chemistry of the cyclo-(P(5)tBu(4))(-) ion: monomeric and oligomeric copper(I), silver(I) and gold(I) complexes.
[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.
Gómez-Ruiz
Santiago
S
Institut für Anorganische Chemie der Universität Leipzig, Leipzig, Germany.
Wolf
Robert
R
Bauer
Sebastian
S
Bittig
Henry
H
Schisler
Andrea
A
Lönnecke
Peter
P
Hey-Hawkins
Evamarie
E
D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006046:Gold / Q000737:chemistry*; D006573:Heterocyclic Compounds, 1-Ring / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000737:chemistry*; D012834:Silver / Q000737:chemistry*; D013237:Stereoisomerism
D006573:Heterocyclic Compounds, 1-Ring; D007477:Ions; D009942:Organometallic Compounds; D009943:Organophosphorus Compounds; D012834:Silver; D006046:Gold; D003300:Copper