1.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).
Blake CJ1, Cook VC, Keniry MA, Kitto HJ, Rae AD, Swiegers GF, Willis AC, Zank J, Wild SB. Inorg Chem. 2003 Dec 29;42(26):8709-15.
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.
2.Photoluminescence properties of four-coordinate gold(I)-phosphine complexes of the types [Au(diphos)2]PF6 and [Au2(tetraphos)2](PF6)2.
Delfs CD1, Kitto HJ, Stranger R, Swiegers GF, Wild SB, Willis AC, Wilson GJ. Inorg Chem. 2003 Jul 14;42(14):4469-78.
Numerous reports describe the photoluminescence of two- and three-coordinate gold(I)-phosphine complexes, but emission in their analogous four-coordinate complexes is almost unknown. This work examines the luminescence of tetrahedral gold(I) complexes of the types [Au(diphos)(2)]PF(6) (diphos = 1,2-bis(diphenylphosphino)ethane, 1) and [Au(2)(tetraphos)(2)](PF(6))(2) (tetraphos = (R,R)-(+/-)/(R,S)-1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane, (R,R)-(+/-)/(R,S)-2). Although nonemitting in solution, these complexes luminesce with an intense yellow color (lambda(max) 580-620 nm) at 293 K in the solid state or when immobilized as molecular dispersions within solid matrixes. The excited-state lifetimes of the emissions (tau 4.1-9.4 micros) are markedly dependent on the inter- and intramolecular phenyl-phenyl pairing interactions present. At 77 K in an ethanol glass, two transitions are observed: a minor emission at lambda(max) 415-450 nm and a major emission at lambda(max) 520-595 nm.
3.A novel linkage-isomeric pair of dinuclear Pd(II) complexes bearing a bis-bidentate tetraphos ligand.
Fessler M1, Czermak G, Eller S, Trettenbrein B, Brüggeller P, Bettucci L, Bianchini C, Meli A, Ienco A, Oberhauser W. Dalton Trans. 2009 Mar 14;(10):1859-69. doi: 10.1039/b815392b. Epub 2009 Jan 27.
The tetraphosphane all trans tetrakis-(di(2-methoxyphenyl)phosphanyl)cyclobutane) (o-MeO-dppcb) has been employed to coordinate metal dichlorides (metal = Ni(II), Pd(II) and Pt(II)), stereoselectively yielding the dinuclear complexes [Ni(2)Cl(4)(micro-(kappaP(1):kappaP(2):kappaP(3):kappaP(4)-o-MeO-dppcb))] and [Pt(2)Cl(4)(micro-(kappaP(1),kappaP(2):kappaP(3),kappaP(4)-o-MeO-dppcb))], characterized by two six and two five-membered metallacycles, respectively. Conversely, the reaction with PdCl(2) led, under comparable synthetic conditions, to the formation of the linkage-isomeric pair [Pd(2)Cl(4)(micro-(kappaP(1),kappaP(2):kappaP(3),kappaP(4)-o-MeO-dppcb))] and [Pd(2)Cl(4)(micro-(kappaP(1):kappaP(2):kappaP(3):kappaP(4)-o-MeO-dppcb))] in a ca. 4 : 1 ratio. The compounds obtained have been characterized in solution by multinuclear NMR spectroscopy and in the solid state by CP-MAS NMR spectroscopy, XRPD and single crystal X-ray diffraction. Compounds and have been tested as catalyst precursors for the CO-ethene-propene co-and terpolymerization in water-acetic acid mixtures.