The preparation and properties of metallofluorene complexes of transition metals.

Metalluorene complexes (π-C₅H₅)M(CO)(C₁₂H₈) (IVa)-(IVc) and (π-C₅H₅) (CO)(C₁₂F₈) (IVd)-(IVf) (M = Co, Rh and Ir) have been prepared from reactions of the appropriate (π-cyclopentadienyl) carbonylmetal diiodides with 2,2′-dilithhiolbiphenyl (IIa) and 2,2′-dilithiooctafluorobiphenyl (IIb), respectively The triphenylphoshine substitution reactions of cobalt compounds (IVa) and (IVd) have also been studied. Reaction of (IIa) and (IIb) with norbornadieneplatinum dichloride result in the preparation of metallocyclic platinum compounds (π-C₇H₈) and (π-C₇H₈)Pt(C₁₂H₈). A reaction of (IIb) with zirconocene dichloride produces (π-C₅H₅)₂Zr(C₁₂F₈), the first example of a ziconium-containing metalofluorene.     

Reactions involving transition metals : XIX. Some reactions of perfluoronorbornadiene with low valent transition metal complexes

Perfluoronorbornadiene reacts with the compounds [M(PPh₃)₄] (M = Pt, Pd) and [IrCl(CO)(PMePh₂)₂] to give the adducts [(C₇F₈)M(PPh₃)₂] and [(C₇F₈)IrCl(CO)(PMePh₂)₂] in which one of the double bonds is coordinated to the metal atom. The platinum complex reacts further with [Pt(PPh₃)₄] to give [(C₇F₈){Pt(PPh₃)₂}₂] having both double bonds coordinated to a Pt atom. The carbonylmetal anions [M^?] react to form the mono-substitution products [(C₇F₇)M] (M = Mn(CO)₅, Re(CO)₅, Ir(CO)₂(PPh₃)₂, Rh(CO)₂(PPh₃)₂), but the use of an excess of [Fe(CO)₂(η-C₅H₆)]^? leads to substitution of one fluorine atom on each of the double bonds. The complex having M = Mn(CO)₅ reacts with [Pt(PPh₃)₄] to afford the derivative [(C₇F₇){Mn(CO)₄(PPh₃)}{Pt(PPh₃)₂}], and the compound where M = Ir(CO)₂(PPh₃)₂ undergoes an oxidative addition reaction with acetyl chloride. Oxidative coupling products have been isolated on UV irradiation of a mixture of perfluoronorbornadiene and [Fe(η⁴-CH₂CRCHCH₂)(CO)₃] (R = H, Me), and under similar conditions the reaction with Fe(CO)₅ affords [(C₇F₈)Fe(CO)₄] in very low yield.     

Self-assembly of a novel pentanuclear centred-tetrahedral silver species

The reaction of 3,6-di(2-pyridyl)-4-trimethylsilylpyridazine with silver(I) tetrafluoroborate gives the pentanuclear complex cation [Ag(5)L(4)](5+), in which the silver centres are arranged as a centred tetrahedron.     

Axiomatization of quantum logics

Starting with a quantum logic (a -orthomodular poset)L, a set of probabilistically motivated axioms is suggested to identifyL with a standard quantum logicL(H) of all closed linear subspaces of a complex, separable, infinite-dimensional Hilbert space. Attention is paid to recent results in this field.     

Remarks on a Constrained Optimization Problem for the Ginibre Ensemble

We study the limiting distribution of the eigenvalues of the Ginibre ensemble conditioned on the event that a certain proportion lie in a given region of the complex plane. Using an equivalent formulation as an obstacle problem, we describe the optimal distribution and some of its monotonicity properties.     

On the description of symmetry of OD structures (III). Short symbols for OD groupoid families

Two kinds of short symbols are proposed: 1. The short symbol of any OD groupoid-family consists of two parts: the symbol for the point group of the groupoid of partial symmetry operations and the symbol for the layer group. No information on the parameters is given. 2. The short symbol of any OD groupoid-family consists of those parts that correspond to the lines of the full symbol. There is, however, only one of the partial symmetry operations given, which transform a layer into an adjacent layer. These short symbols are suitable for storage of the symmetry data of OD structures in computer operated data banks.