Homochiral Self Recognition in Gold-Phosphane-Helicates

Schuh, Walter; Kopacka, Holger; Wurst, Klaus; Péringer, Paul

doi:10.1002/1099-0682(200208)2002:8<2202::aid-ejic2202>3.0.co;2-g

Cited by 15 publications

(4 citation statements)

References 16 publications

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“…The twist of each enantiomer of the cation in the structure is due solely to the twist of the central TBCB ring (Figure ). In contrast, the centrosymmetrical cation of [Au 4 {( R *, S *)-tetraphos} 2 ](OTf) 4 ·EtOH contains two pairs of roughly linear P−Au−P interactions (angles: outer 171.0(2), inner 168.0(2)) between the two ligand strands, which have the head-to-head arrangement . Because of the constraints of the central ten-membered ring in the structure, which has a centrosymmetrical chairlike conformation, the R ends of the two phosphine strands generate a terminal ten-membered ring of λ conformation and the S ends a ring of δ conformation in the centrosymmetrical cation.…”

Section: Resultsmentioning

confidence: 99%

“…The complex 2)) between the two ligand strands, which have the head-to-head arrangement. 7 Because of the constraints of the central ten-membered ring in the structure, which has a centrosymmetrical chairlike conformation, the R ends of the two phosphine strands generate a terminal tenmembered ring of λ conformation and the S ends a ring of δ conformation in the centrosymmetrical cation. The oppositely chiral relationship of these rings corresponds to the oppositely chiral relationships of the chiral metal stereocenters in the digold complex.…”

Section: Introductionmentioning

confidence: 99%

“…Here we describe our findings concerning the self-assembly of double-stranded disilver(I) and digold(I) complexes of the fully flexible, achiral , tetratertiary phosphine ( R *, S *)-tetraphos. A recent paper describes the synthesis and crystal and molecular structures of tetra gold(I) helicates of ( R *, R *)-(±)- and ( R *, S *)-tetraphos …”

Section: Introductionmentioning

confidence: 99%

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Diastereoselectivity and Molecular Recognition in the Self-Assembly of Double-Stranded Dinuclear Metal Complexes of the Type [M₂{(R,S)-tetraphos}₂](PF₆)₂ (M = Ag and Au)

et al. 2003

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The ligand (R,S)-Ph(2)PCH(2)CH(2)P(Ph)CH(2)CH(2)P(Ph)CH(2)CH(2)PPh(2), (R,S)-tetraphos, combines with silver(I) and gold(I) ions in the presence of hexafluorophosphate to diastereoselectively self-assemble the head-to-head (H,H) diastereomers of the double-stranded, dinuclear metal complexes [M(2)[(R,S)-tetraphos](2)](PF(6))(2) in which the two chiral metal centers in the complexes have M (R end of phosphine) and P (S end of phosphine) configurations. The crystal and molecular structures of the compounds have been determined: (H,H)-(M,P) -[Ag(2)[(R,S)-tetraphos](2)](PF(6))(2), monoclinic, P2(1)/c, a = 10.3784(2), b = 47.320(1), c = 17.3385(4) A, beta = 103.8963(5) degrees, Z = 4; (H,H)-(M,P)-[Au(2)[(R,S)-tetraphos](2)](PF(6))(2), monoclinic, P.2(1) (No. 4, c unique axis), a = 24.385(4), b = 46.175(3), c = 14.820(4) A, Z = 8. The complexes crystallize as racemic compounds in which the unit cell in each case contains equal numbers of enantiomorphic molecules of the cation and associated anions. The cations in both structures have similar side-by-side structures of idealized C(2) symmetry, the bulk helicity of each molecule in the solid state being due solely to the twist of the central ten-membered ring containing the two metal ions of opposite configuration, which has the chiral twist-boat-chair-boat conformation. When 1 equiv each of (R,S)-tetraphos, (R,R)-(+/-)-tetraphos, (S,S)-(+)-tetraphos, 2 equiv of Ph(2)PCH(2)CH(2)PPh(2) (dppe), and 7 equiv of [AuCl(SMe(2))] in dichloromethane are allowed to react for several minutes in the presence of an excess of ammonium hexafluorophosphate in water (two phases), the products are the double-stranded digold(I) complexes in which each ligand strand has recognized itself by stereoselective self-assembly, together with [Au(dppe)(2)]PF(6).

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Diastereoselectivity and Molecular Recognition in the Self-Assembly of Double-Stranded Dinuclear Metal Complexes of the Type [M₂{(R,S)-tetraphos}₂](PF₆)₂ (M = Ag and Au)

et al. 2003

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“…Upon irradiation at 313 or 366 nm, Pd()-Re()-containing tetranuclear squares undergo photoisomerization and convert to their corresponding dinuclear complexes whereas Pt()-Re()-based squares only show slow square disassembling processes. 78 A molecular triangle of palladium() 79 was synthesised from the ligand 4(3H )-pyrimidone (HL 93 ) and forms a bowl-like molecular triangle, [{Pd-(bu 2 bipy)(µ-L 93 )} 3 ] 3ϩ (bu 2 bipy = 4,4Ј-di-tert-butyl-2,2Јbipyridine), with the deprotonated ligand (L 93 ). This triangular complex acts as a host for binding of several anionic guests including nitrate, HSO 3 Ϫ , percholorate and triflate.…”

Section: Cages and Related Complexesmentioning

confidence: 99%

18 Macrocyclic and supramolecular coordination chemistry

Cronin

2003

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Hexa‐ and Octagold Chains from Flexible Tetragold Molecular Units Supported by Linear Tetraphosphine Ligands

et al. 2009

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Flexibler Baustein: Flexible kettenförmige Tetragold(I)‐Komplexe wurden mithilfe eines neuen Tetraphosphanliganden mit Methylenbrücken hergestellt und durch Umsetzung mit KI oder NaAuCl4 in den längeren linearen Octagold(I)‐Komplex {Au8} bzw. die cyclische Hexagold(I)‐Struktur {Au6} überführt (siehe Bild; Au magenta, Cl dunkelgrün, PF6 hellgrün, I rosa). Die Tetragoldkomplexe lumineszieren überdies bei Raumtemperatur.magnified image

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Homochiral Self Recognition in Gold-Phosphane-Helicates

Cited by 15 publications

References 16 publications

Diastereoselectivity and Molecular Recognition in the Self-Assembly of Double-Stranded Dinuclear Metal Complexes of the Type [M₂{(R,S)-tetraphos}₂](PF₆)₂ (M = Ag and Au)

Diastereoselectivity and Molecular Recognition in the Self-Assembly of Double-Stranded Dinuclear Metal Complexes of the Type [M₂{(R,S)-tetraphos}₂](PF₆)₂ (M = Ag and Au)

18 Macrocyclic and supramolecular coordination chemistry

Hexa‐ and Octagold Chains from Flexible Tetragold Molecular Units Supported by Linear Tetraphosphine Ligands

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Homochiral Self Recognition in Gold-Phosphane-Helicates

Cited by 15 publications

References 16 publications

Diastereoselectivity and Molecular Recognition in the Self-Assembly of Double-Stranded Dinuclear Metal Complexes of the Type [M2{(R*,S*)-tetraphos}2](PF6)2 (M = Ag and Au)

Diastereoselectivity and Molecular Recognition in the Self-Assembly of Double-Stranded Dinuclear Metal Complexes of the Type [M2{(R*,S*)-tetraphos}2](PF6)2 (M = Ag and Au)

18 Macrocyclic and supramolecular coordination chemistry

Hexa‐ and Octagold Chains from Flexible Tetragold Molecular Units Supported by Linear Tetraphosphine Ligands

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Product

Resources

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Diastereoselectivity and Molecular Recognition in the Self-Assembly of Double-Stranded Dinuclear Metal Complexes of the Type [M₂{(R,S)-tetraphos}₂](PF₆)₂ (M = Ag and Au)

Diastereoselectivity and Molecular Recognition in the Self-Assembly of Double-Stranded Dinuclear Metal Complexes of the Type [M₂{(R,S)-tetraphos}₂](PF₆)₂ (M = Ag and Au)