Aleksandr I. Yanovsky

Complexation of [ω-diphenylphosphinoalkyl]diphenylphosphine sulphides with AgNO3

By reaction of [ ω -diphenylphosphinoalkyl]diphenylphosphine sulphides Ph 2 P(CH 2 ) n P(S)Ph 2 ( n = 2–4) (L 1 −L 3 ) with AgNO 3 in CH 3 CN crystalline complexes with the composition metal:ligand 1:1 [Ag(L 1 )NO 3 , Ag(L 2 )NO 3 , Ag(L 3 )NO 3 ] and 1:2 [Ag(L 1 ) 2 NO 3 , Ag(L 3 ) 2 NO 3 ] were isolated. According to the X-ray analysis data, the crystals of Ag(L 1 )NO 3 are constructed from centrosymmetric dimeric molecules based on the 12-membered macrocycle AgSPCH 2 CH 2 PAgSPCH 2 CH 2 P ¯ . Each of the neutral ligands L 1 is a bridge between two silver ions and each of the silver ions is coordinated by a chelating NO 3 group. According to the IR spectra, the other 1:1 complexes also have an analogous structure. In the 1:2 complexes the coordinated NO 3 groups of the 1:1 complexes are replaced by the phosphine sulphide ligand. The downfield shifts of the signals of P III and P V atoms in 31 P NMR spectra of 1:2 complexes in comparison with the free ligands L 1 and L 3 reflect a participation of the P III atom and P=S group in complex formation.

Carbon–carbon bond formation by alkyne–µ,η2-acetylide and alkyne–CO coupling in the reaction of (OC)5MCCPH (M = MN, Re) with HOs3(CO)10(µ,η2-CCPh). X-Ray structure of HOs3Re(CO)14(C2Ph)2

Addition of (OC)5MCCPh (M = Mn,Re) to HOs3(CO)10(µ,η2-CCPh) leads to the formation of carbon–carbon bonds under mild conditions to yield metal cluster compounds HOs3M(CO)14(C2Ph)2; the cluster HOs3Re(CO)14(C2Ph) has been characterized by an X-ray structure analysis.

X-ray structure and fluxional behaviour of N,N′-di-p-fluorophenyltriazenido complex of nickel(II)

The Ni(II) triazenide complex, trans -( o -Tol)Ni(PEt 3 ) 2 N 3 Ar 2 (Ar= p -FC 6 H 4 ) ( 1 ), was synthesized by the reaction of trans -( o -Tol)Ni(PEt 3 ) 2 Br with Ar 2 N 3 Na. The crystal structure as well as the 1 H-, 19 F- and 31 P-NMR spectra in toluene- d 8 at different temperatures are reported. It was found that the triazenido group acts as a monodentate ligand. Complex 1 in solid state has a S - cis -structure with NiN(3) σ-bond and exists as a 3:1 mixture of two isomers with cisoid or transoid orientation of the Me group of the o -tolyl ligand relative to the N(1)N(2) bond. It was established that the N , N ′-migration of ( o -Tol)Ni(PEt 3 ) 2 group occurs in a solution of 1 . The migration rate increases with the temperature increase in the range from −104 to −45°C. However, a further increase in the temperature slows down the process.

Alkylcobalt chelates with Schiff bases derived from a β-diketone bearing both alkyl and aryl groups

Abstract Organocobalt(III) complexes with Schiff bases derived from a β -diketone bearing both an alkyl and an aryl group have been prepared. The template syntheses using benzoylacetone and ethylenediamine as complexing agents provide a route to alkylcobalt chelates with the corresponding tri- and tetradentate Schiff bases. However, if a β -diketone with two aryl groups, e.g. dibenzoylmethane, was employed as the starting ketoenol component, no organometallic products were detected; a new mixed-ligand ‘inorganic’ chelate of cobalt(II), [Co{O=C(Ph)CH=C(Ph)O} 2 (en)], was isolated instead. Its structure as well as that of one of the alkylcobalt complexes with a tridentate Schiff base composed of benzoylacetone and ethylenediamine have been established by X-ray techniques. The current scope of the template synthesis of alkylcobalt complexes with Schiff bases is summarized.

Synthesis, solution behaviour and molecular structures of 16-electron closo-2-(Ph3P)-1-N,2-[μ-(η2-CH2CHCh2)]-1-N-(σ-CH2CHCH2)-2,1- RhCB10H10, the first η2-olefinic monocarbon metallacarborane

The first η 2 -olefinic monocarbon metallacarbone closo -2-(Ph 3 P)-1-N,2-[ μ -( η 2 -CH 2 CHCh 2 )]-1-N-( σ -CH 2 CHCH 2 )-2,1- RhCB 10 H 10 has been prepared by the reaction of the dimeric anion {[Ph 3 PRhB 10 H 10 CNH 2 ] 2 -μ-H} − [PPN] + with allyl bromide and characterized by a combination of spectroscopic methods and a single-crystal X-ray diffraction study. The variable temperature 1 H and 13 C NMR studies revealed the fluxional behavior of the η 2 -olefinic complex in CD 2 Cl 2 solution which is associated with the allyl side-chain exchange process.