Jörg J. Schneider

Transition metal complexes VII. [(η5-Cp)Ni(PEt3)]2, a dinuclear organometallic complex with an unbridged NiNi bond; structure and heteronuclear complexes thereof

[(η 5 -Cp)Ni(PEt 3 )] 2 ( 1 ) has been synthesized by reacting (η 5 -Cp)Ni(PEt 3 )Cl with activated magnesium. 1 contains an unbridged nickelue5f8nickel bond. Reaction of 1 with elemental sulfur yields the clusters [(η 5 -Cp) 2 (PEt 3 ) 2 (μ 3 - S)Ni 3 ] ( 2 ) and [(η 5 -Cp)(PEt 3 )Ni(μ-S)Ni(η 5 -Cp)] 2 ( 3 ). The homologous selenium compound [(η 5 -Cp)(PEt 3 )Ni(μ- Se)Ni(η 5 -Cp)] 2 ( 4 ) has been obtained by the reaction of 1 with elemental selenium. 1 reacts with tellurium by insertion to yield {[(η 5 -Cp)Ni(PEt 3 )] 2 Te} ( 5 ). Tin(II) chloride can also be inserted into the nickelue5f8nickel bond of 1 to give {[(η 5 -Cp)Ni(PEt 3 )] 2 SnCl 2 } ( 6 ). Both chlorine atoms in 6 react with alkyllithium to give compounds of the type {[(η 5 -Cp)Ni(PEt 3 )] 2 SnR 2 } ( 7 ) ( a : Rue5fbMe, b : Rue5fbn-Bu). The reaction of 6 with activated magnesium yields {[(η 5 -Cp)Ni(PEt 3 )] 3 SnCl} ( 8 ). Crystal structures of 1, 2, 3, 5, 6 and 8 have been determined.

Transition metal complexes: VIII. An unusual rearrangement of a butadienyl ligand via cyclometallation☆

A transition metal complex which is a bis-arylimine pyridine MXn complex or a [bis-arylimine pyridine MXp+][NC−]q complex comprising a bis-arylimine pyridine ligand and M is a transition metal atom; n matches the formal oxidation state of the transition metal atom M; X is halide, optionally substituted hydrocarbyl, alkoxide, amide, or hydride; NC− is a non-coordinating anion; and p+q matches the formal oxidation state of the transition metal atom M. The transition metal complexes of the present invention, their complexes with non-coordinating anions and catalyst systems containing such complexes have good solubility in non-polar media and chemically inert non-polar solvents especially aromatic hydrocarbon solvents. The catalyst systems can be used for a wide range of (co-)oligomerization, polymerization and dimerization reactions.Abstract Cp★Ni(η 1 ,η 2 -C 4 HPh 4 ) (Cp★ = η 5 -C 5 -Me 5 ) ( 1 ) was prepared by reacting Cp★Ni(acac) with 1,4-dilithium-1,2,3,4-tetraphenylbutadiendiyl and its structure determined by X-ray diffraction. Thermolysis of 1 in THF affords Cp★Ni(η 3 -1-benzyl-2,3-diphenylindenyl) ( 2 ) and Cp★Ni(η 3 -3-benzylyl-1,2-diphenylindene) ( 3 ). The structures of 2 and 3 were also determined by X-ray diffraction. A proposed mechanism of product formation is discussed.

Metal atoms in the synthesis of metal clusters: III. HFe3(CO)9(CCSiMe3), synthesis and crystal structure☆

Abstract Vaporization of nickel atoms into a solution of bis(trimethylsilyl)acetylene and Fe(CO)5 in methylcyclohexane at −120°C unexpectedly afford (after chromatographic work-up and crystallization) deep red crystals of the new triangular cluster μ3-(δ,2π-trimethylsilylacetylene)tris[(tricarbonyl)iron]hydride 1 in low yield.