Search

Norbornene based monomers containing the 2-phenylpyridinato–N,C2′ platinum(II) complex bonded by acetylacetonate or pyrazolonate anchor groups were synthesized and copolymerized with a carbazole-containing norbornene comonomer by ring-opening metathesis polymerization (ROMP). The photo- and electroluminescence spectra of the resulting Pt-copolymers are similar. They consist of broad bands with maxima at 495, 530 and 565 nm which arise from the mixed ligand centered (LC) and metal to ligand charge transfer (MLCT) transitions. The copolymer with the cyclometalated platinum(II) complex bonded to the polymer chain via the pyrazolonate anchor group revealed the highest brightness of electroluminescence (260 cd/m2 at 21 V).

Bimetallic alkylidene complexes of molybdenum (RF3O)2(ArN)Mo CH–SiMe2–CH Mo(NAr)(ORF3)2 (1) and (RF3O)2(ArN)Mo CH–SiPhVin–CH Mo(NAr)(ORF3)2 (2) (Ar = 2,6- Pr 2 i C6H3; RF3 = CMe2CF3) have been prepared by the reactions of vinyl silicon reagents Me2Si(CH CH2)2 and PhSi(CH CH2)3 with known alkylidene compound PhMe2C–CH Mo(NAr)(ORF3)2. Complexes 1 and 2 were structurally characterized. Ring opening metathesis polymerization (ROMP) of cyclooctene using compounds 1 and 2 as initiators led to the formation of high molecular weight polyoctenamers with predominant trans-units content in the case of 1 and predominant cis-units content in the case of 2.

Bimetallic alkylidene complexes of tungsten (R′O)2(ArN)W CH–SiR2–CH W(NAr)(OR′)2 (R = Me (1), Ph (2)) and (R′O)2(ArN)W CH–SiMe2SiMe2–CH W(NAr)(OR′)2 (3) (Ar = 2 , 6 – Pr 2 i C 6 H 3 ; R′ = CMe2CF3) have been prepared by the reactions of divinyl silicon reagents R2Si(CH CH2)2 with known alkylidene compounds R′′–CH Mo(NAr)(OR′)2. (R′′ = But, PhMe2C) Complexes 1–3 were structurally characterized. Ring opening metathesis polymerization (ROMP) of cyclooctene using compounds 1–3 as initiators led to the formation of high molecular weight polyoctenamers with predominant trans-units content in the case of 1 and 3 and predominant cis-units content in the case of 2.

Alkylidene complex of tungsten Me3Ge-CH W(NAr)(OCMe2CF3)2 (1) ( Ar = 2 , 6 - Pr 2 i C 6 H 3 ) has been prepared by the reaction of Me3GeCH CH2 with known alkylidene compound But–CH Mo(NAr)(OCMe2CF3)2 at a molar ratio 1:1. Metallacycle [CH(GeMe3)CH(GeMe3)CH2]W(NAr)(OCMe2CF3)2 (2) was isolated from the same reaction when twofold excess of Me3GeCH CH2 was used. The both compounds 1 and 2 were structurally characterized. They were found to have low activity in metathesis of 1-hexene and high activity in ROMP of cyclooctene and norbornene.

The novel silicon-, germanium- and tin-containing imido alkyl complexes of tungsten of the type (ArN)2W(CH2EMe3)2 ( Ar = 2 , 6 - Pr 2 i C 6 H 3 ; E = Si (1), Ge (2), Sn (3)) have been prepared by the reactions of (ArN)2WCl2(dme) (dme = 1,2-dimethoxyethane) with heteroelement-containing alkyllithium or Grignard reagents Me3ECH2Li (E = Si, Ge), Me3ECH2MgCl (E = Ge, Sn). The title compounds were isolated in high yields as crystalline solids and characterized by elemental analysis, IR, 1H, 13C, 29Si and 119Sn NMR spectroscopy and X-ray diffraction studies. The geometry of the W atoms in the compounds can be described as a distorted tetrahedron.

Alkylidene complex of molybdenum Ph3Si–CH Mo(NAr)(OCMe2CF3)2 (1) ( Ar = 2 , 6 - Pr 2 i C 6 H 3 ) has been prepared by the reaction of Ph3SiCH CH2 with known alkylidene compounds Alkyl-CH Mo(NAr)(OCMe2CF3)2 (Alkyl = But, PhMe2C). According to X-ray diffraction studies the geometry of the Mo atom in (1) can be described as a distorted tetrahedron. Reactions of heteroelement-containing imido alkyl compounds of molybdenum and tungsten (ArN)2M(CH2EMe3)2 ( Ar = 2 , 6 - Pr 2 i C 6 H 3 ; M = Mo. W; E = Si, Ge, Sn) with triflic acid were shown to yield a complex mixture of products among which carbene complexes have not been observed. The formation of carbene complexes of tungsten in low yields was observed by 1H NMR spectroscopy in the reactions of (ArN)2W(CH2EMe3)2 (E = Si, Ge, Sn) with hydrogen chloride in THF-d8. Catalytic properties of heteroelement-containing alkylidene complexes of molybdenum R3E–CH Mo(NAr)(OCMe2CF3)2 (E = Si, Ge; R = Me, Ph) and also hydrocarbon analogs Alkyl-CH Mo(NAr)(OCMe2CF3)2 (Alkyl = But, PhMe2C) in metathesis of 1-hexene were investigated. The catalytic activity of alkylidene complexes was shown to depend essentially on the nature of substituent bonded to carbene carbon atom.

The novel germanium-containing alkylidene complexes of molybdenum R3Ge–CH Mo(NAr)(OCMe2CF3)2 (Ar = 2,6-i-Pr2C6H3; R = Me, Ph) have been prepared by the reaction of organogermanium vinyl reagents R3 GeCH CH2 with known alkylidene compounds Alkyl–CH Mo(NAr)(OCMe2CF3)2 (Alkyl = But, PhMe2C). The titled compounds were isolated as crystalline solids and characterized by elemental analysis, 1H NMR, 13C NMR spectroscopy and X-ray diffraction studies. The geometry of the Mo atoms in the compounds can be described as a distorted tetrahedron.