Faouzi Bouachir

Darstellung und eigenschaften von und reaktionen mit metallhaltigen heterocyclen: XXV. Synthese und eigenschaften neuer platina- und rhodacycloalkane durch substitution und oxidative addition einer CCl-bindung

The platinacyclopentane derivative [Cl(CH2)3R2P](Cl)PtPR2CH2CH2CH2 is formed by action of Cl(CH2)3PR2 on Pt(COD)2 in n-hexane via the not isolable Pt[PR2(CH2)3Cl]2 (R  C6H11) by oxidative addition of a CCl bond to platinum. [μ-CIRh(CO)2]2 reacts in benzene with Cl(CH2)3PR2 under partially CO substitution to give the stable intermediate Cl(OC)Rh[PR2(CH2)3Cl]2. In boiling toluene oxidative addition of a CCl bond to rhodium occurs under formation of the phospharhodacyclopentane [CI(CH2)3R2P] Cl2(OC)-RhPR2CH2CH2CH2 (R  C6H5). The 31P{1H}-NMR spectra of the rhodium compound is characterized by an ABX system, that of the platinum by superposition of an ABX pattern with an AB spectrum.

Darstellung und eigenschaften von und reaktionen mit metallhaltigen heterocyclen XXII. Synthese, eigenschaften und kristallstruktur des sechsgliedrigen heterocyclus [(h5-C5H5)NiSP(CH3)2]2 und dessen verhalten gegenüber alkinen

The heterocycle [( h 5 -C 5 H 5 )NiSP(CH 3 ) 2 ] 2 is obtained by treatment of ( h 5 -C 5 H 5 ) 2 Ni with (CH 3 ) 2 HPS in toluene and crystallizes monoclinic in the space group P 2 1 / c with Z = 2. The highly reactive three-membered ring ( h 5 -C 5 H 5 ) (CH 3 ) 2 which is a dissociation product of [( h 5 -C 5 H 5 )NiSP(CH 3 ) 2 ] 2 , can be trapped with bis(methoxycarbonyl)acetylene to give the PS containing nickelacyclopentadiene ( h 5 -C 5 H 5 ) R (R  CO 2 CH 3 ).

Cationic methallylnickel(II) complexes with α-diimine ligands: synthesis and X-ray structure

The α-diimine ligands ArNC(R)C(R)NAr react with Ni(COD) 2 ( 2 ) in the presence of methallyloxyphosphonium hexafluorophosphate [CH 2 C(Me)CH 2 OP(NMe 2 ) 3 ] + ·PF 6 − ( 3 ) to give new cationic methallyl complexes of nickel(II) with α-diimine ligands 4a and 4b . The same complexes 4a – d can also be generated in high yields by reacting [α-diimine] NiBr 2 with zinc and methallyloxyphosphonium salt 3 . Molecular structure of 4a was determined by a single-crystal X-ray diffraction.