Yang Jie Wu

Synthesis, characterization and structure of ferrocenylketimine complexes of platinum(II)

Abstract The reactions of ferrocenylketimines [(η5-C5H4CMe=NAr)Fe(η5-C5H5)] (Ar = a variety of substituted phenyls) with cis-Pt(DMSO)2Cl2 in refluxing toluene have led to the formation of both the five-membered cycloplatinated derivatives [σ-Pt(η5-C5H3CMe=NAr)Fe(η5-C5H5)(DMSO)Cl] in the presence of sodium acetate and the coordinated compounds [trans-PtCl2(DMSO)(η5-C5H4CMe=NAr)Fe(η5-C5H5)] in the absence of sodium acetate. The compounds have been characterized by elemental analysis, IR, 1H NMR and two-dimensional NOESY spectra. The X-ray crystal structures of [σ-Pt(η5-C5H3CMe=NPh)Fe(η5-C5H5)(DMSO)Cl] and [trans-PtCl2(DMSO)(η5-C5H4CMe=NPh)Fe(η5-C5H5)] have been determined.

Cyclometallation of ferrocenylimines: Part II. Studies on the cyclomercuration of [1-(arylimino)ethyl] ferrocenes and related structure-reactivity relationships1

Abstract A series of 2-chloromercurio-1-[1-(arylimino)ethyl]ferrocenes has been synthesized by direct mercuration of the corresponding ferrocenylketimines. Competitive coordination and protonation processes are proposed and the effect of the structures of ferrocenylketimines on the mercuration reactivities discussed. A relatively strong intramolecular coordination between the imino nitrogen and mercury in the molecules of the 2-mercurated products was indicated by the X-ray crystal structure analysis of 2-chtoromercurio-1-[1-[(4-chlorophenyl)imino]ethyl]ferrocene, in which the distance between the mercury and the nitrogen is 2.766 A, significantly shorter than the sum of the Van der Waals radii of mercury and nitrogen, 3.05–3.15 A.

TRANSMETALLATION REACTIONS OF PLANAR CHIRAL CYCLOPALLADATED FERROCENYLIMINES WITH METALLIC MERCURY

Abstract A series of optically active 2-chloromercurio-1-[1-(arylimino)ethyl] ferrocenes was synthesized by transmetallation of optically active cyclopalladated ferrocene derivatives with metallic mercury. The structure and absolute configuration of complexes Rp- 4b were determined by X-ray diffraction, on the basis of which and the CD spectra the absolute configuration of other optically active compounds was ascertained.

CRYSTAL STRUCTURES OF ANIL OF BENZOYLFERROCENE AND ITS DERIVATIVE OF MERCURY : SPECIFIC ARRANGEMENT OF THE FERROCENYL AND PHENYL GROUPS AROUND THE CN BOND

Abstract The crystal structures of [(phenylimino) phenylmethyl]ferrocene ( 1 ) and 2-chloromercurio-1-[(phenylimino)phenylmethyl]ferrocene ( 2 ) have been determined by X-ray diffraction methods to obtain structural information on the anils of benzoylferrocene and their mercurated derivatives. The most striking feature is the specific arrangements of the phenyl and cyclopentadienyl rings around the CN bond. It has been found that the N -phenyl ring adopts a trans conformation with the ferrocenyl moiety, and the twist angles of both the N -phenyl and C -phenyl rings out of the plane of CN bond are much larger than that of the s substituted ferrocenyl ring out of this plane. A comparison between the structures of 1 and 2 is presented. The intramolecular coordination between the Hg and N in compound 2 is confirned, showing an NHg distance of 2.870 A, shorter than the sum of van der Waals radii of N and Hg (3.05–3.15 A).

CYCLOMETALLATION OF FERROCENYLIMINES III. REGIOSELECTIVITY IN HG(II) CYCLOMETALLATED COMPLEXES

Abstract The synthesis and mercuration of a series of Schiff bases 1′-benzoyl-1-[(arylimino)phenylmethyl]ferrocene (aryl: a variety of substituted phenyls) have been studied. In all cases the mercuration occurred at the 2-position of the ferrocene ring. Oxygen → mercury coordinated products were not obtained. The X-ray crystal structure of [2-chloromercurio-l-[((phenylimino)phenylmelhyl)-l′-benzoyl] ferrocene 5c has been determined; this crystallizes in the monoclinic, space group P2 1 / c with a = 10.168(3), b = 16.105(3), c = 15.463(4) A, β = 103.61(2)° and Z = 4. Refinement of atomic parameters gave an R factor of 0.038 ( Rω = 0.055) for 2440 unique reflections having I > 3 σ ( I ). The structure confirms the formation of a five-membered metallocycle on the ferrocene moiety.

Synthesis of cylopalladated anils of benzoylferrocene via transmetallation reaction of mercurated ferrocenylketimines with Li2PdCl4 or by direct cyclopalladation reaction of ferrocenylketimines

Abstract A series of cyclopalladated anils of benzoylferrocene with the general formula [ Pd {(η 5 - C 5 H 5 ) Fe } (η 5 - C 5 H 3 CPh  NAr ) Cl ( PPh 3 )] (Ar = a variety of substituted phenyls and β = napthyl) were synthesized by transmetallation reaction of the corresponding cyclomercurated derivatives [ HgCl {(η 5 - C 5 H 5 } Fe η 5 - C 5 H 3 CPh  NAr ] with lithium tetrachloropalladate or by direct cyclopalladation reaction of the corresponding ferrocenylketimines [(ν5-C5H5)Fe(ν5-C5H4CPh = NAr)], followed by the treatment of the resulting products with triphenylphosphine. The composition and the structure of the metallocycles were characterized by elemental analysis, IR, 1H NMR and two-dimensional NOESY spectra. Some spectral features of these complexes were also discussed.

Studies on the syntheses of hydroxy-bearing benzo-azacrown ethers and their complexing behaviour

Five new hydroxy-bearing dibenzoazacrown ethers were synthesized by a convenient route. Reaction of salicyladehyde with epichlorohydrin gave 1,3-bis(2-formylphenoxy)-2-propanol, which condensed with diamino compounds followed by a one pot reduction of the corresponding bis-imine derivatives without isolation to afford the hydroxy-bearing dibenzoazacrown ethers. All of the ligands were identified by EA, IR and NMR. Some transition metal complexes were prepared and characterized by elemental analysis, IR and molar conductance. The transport of alkali metal cations across a liquid membrane by using these ligands as ion carrier was also studied.

Cyclometallation reaction of 1,1′-bis[1–arylimino)ethyl]ferrocenes with platinum(II)

Abstract The reaction of 1,1′-bis[1–arylimino)ethyl]ferrocenes with cis-Pt(DMSO)2Cl2 in refluxing toluene and in the presence of NaOAc leads to meso and dl stereoisomers of biscyclometallated diplatinum complexes. Some individual stereoisomers were isolated successfully by column chromatography. The composition and the structure of the metallocycles were characterized by elemental analysis, IR and 1H NMR spectroscopy. A mechanism for the formation of stereoisomers in the cycloplatination reaction is suggested.

Transmetallation reaction of cyclomercurated anils of benzoylferrocene with metallic tin.: X-ray crystal structure of [SnCl2{(η5-C5H5)Fe(η5-C5H3CPhNC6H4-4-CH3)}2]

Abstract The transmetallation reaction of cyclomercurated anils of benzoylferrocene [HgCl{( η 5 -C 5 H 5 )Fe( η 5 -C 5 H 3 CPhNAr)}] (Ar=substituted phenyl groups) with metallic tin was carried out in refluxing xylene to give dichlorobisferrocenyltin(IV) [SnCl 2 {( η 5 -C 5 H 5 )Fe( η 5 -C 5 H 3 CPhNAr)} 2 ]. The composition and structure of products were characterized by elemental analysis, IR, 1 H-NMR and 2D NOESY spectra. The molecular structure of [SnCl 2 {( η 5 -C 5 H 5 )Fe( η 5 -C 5 H 3 CPh=NC 6 H 4 -4-CH 3 )} 2 ] was determined by single crystal X-ray analysis. The distances of N and Sn are 2.519(3) and 2.501(3) A, respectively, shorter than the sum of van der Waals radii of N and Sn (3.6 A), indicating an intramolecular coordination of N and Sn. The 119 Sn-NMR spectra were recorded, and a satisfactory linear relationship was found to exist between the 119 Sn shifts ( δ ) and Hammett substituent constants.

Crystal and molecular structure of [1-[(4-chlorophenyl) imino] ethyl] ferrocene and a structural comparison with its cyclometallated derivatives

Abstract The structure of [1-[(4-chlorophenyl)imino]ethyl]ferrocene ( 1 ) has been established by X-ray crystal structure analysis. The most striking feature of the molecule is the twist of the N-phenyl ring out of the plane C C N C by 75.1°, and the perpendicular nature of the N-phenyl ring with respect to the ferrocenyl cyclopentadienyl rings. A structural comparison between 1 , its cyclomercurated derivative 2 and cyclopalladated derivative 3 has been made to find out the relationship between the structure and the properties of 1 and its cyclometallated derivatives.