Late transition metal oxo and imido complexes. 11. Gold(I) oxo complexes

Journal Article · Wed May 12 00:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00062a012· OSTI ID:6236282

Yang, Yi; Ramamoorthy, V; Sharp, P R ^[1]

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1. Univ. of Missouri, Columbia (United States)

Many late transition metals have the ability to dissociatively activate O[sub 2]. The resulting surface oxygen atoms are important catalytic intermediates which can be modeled by oxo compounds. The gold(I) oxo complexes [(LAu)[sub 3]([mu][sub 3]-O)]BF[sub 4] (1) have been prepared for L = PMePh[sub 2], PMe[sub 2]Ph, PEtPh[sub 2], PPr[sup i]Ph[sub 2], P(p-ClPh)[sub 3], P(o-tol)[sub 3], P(OEt)Ph[sub 2], and P(OMe)[sub 3]. Two of these new oxo complexes, as well as a new crystal form of [(PPh[sub 3]Au)[sub 3]([mu][sub 3]-O)]BF[sub 4], were structurally characterized. Crystals of [(PMePh[sub 2]Au)[sub 3]([mu][sub 3]-O)]BF[sub 4][center dot]CH[sub 2]Cl[sub 2] from CH[sub 2]Cl[sub 2]/ether are monoclinic (P2[sub 1]/c) with a = 11.395(2) [Angstrom], b = 25.901(2) [Angstrom], c = 16.024(3) [Angstrom], [beta] = 110.615(8)[degrees], and Z = 4. Crystals of [(PPh[sub 3]Au)[sub 3]([mu][sub 3]-O)]BF[sub 4][center dot]1.5CH[sub 2]Cl[sub 2] from CH[sub 2]Cl[sub 2]/ether are monoclinic (P2[sub 1]/c) with a = 14.723(3) [Angstrom], b = 14.808(3) [Angstrom], c = 25.999(3) [Angstrom], [beta] = 104.06(3)[degrees], and Z = 4. Crystals of [(P(o-tol)[sub 3]Au)[sub 3]([mu][sub 3]-O)]BF[sub 4][center dot]xC[sub 6]H[sub 14][center dot]0.5H[sub 2]O from CH[sub 2]Cl[sub 2]/hexane are monoclinic (P2[sub 1]/a) with a = 14.2611(45) [Angstrom], b = 27.4668(71) [Angstrom], c = 23.0907(81) [Angstrom], [beta] = 91.37(2)[degrees], and Z = 4. The PPh[sub 3] and the PMePh[sub 2] structures consist of inversion-related edge-bridged [(LAu)[sub 3]O][sup +] dimers held together by Au-Au interactions. The P(o-tol)[sub 3] structure consists of isolated [(LAu)[sub 3]O][sup +] units. New oxo complexes are also formed in equilibrium mixtures of [((PPh[sub 3])Au)[sub 3]([mu][sub 3]-O)]BF[sub 4] and LAuCl. Oxygen-17 NMR data for 1 show chemical shifts of +19.7 to [minus]36.0 ppM (H[sub 2]O reference) with upfield shifts corresponding to increasing basicity of the phosphine, L. 17 refs., 1 fig., 4 tabs.

• DOE Contract Number: FG02-88ER13880
• OSTI ID: 6236282
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:10; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BORON COMPOUNDS
CHALCOGENIDES
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
CRYSTALS
EVEN-ODD NUCLEI
FLUORINE COMPOUNDS
FLUOROBORATES
GOLD COMPLEXES
GOLD COMPOUNDS
GOLD OXIDES
HALOGEN COMPOUNDS
ISOTOPES
LATTICE PARAMETERS
LIGHT NUCLEI
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
MONOCLINIC LATTICES
NUCLEAR MAGNETIC RESONANCE
NUCLEI
OXIDES
OXYGEN 17
OXYGEN COMPOUNDS
OXYGEN ISOTOPES
PHOSPHINE OXIDES
PHOSPHINES
PHOSPHORUS COMPOUNDS
RESONANCE
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS