Aluminum complexes incorporating bidentate amido phosphine ligands.

نویسندگان

  • Lan-Chang Liang
  • Mei-Hui Huang
  • Chen-Hsiung Hung
چکیده

A series of aluminum complexes supported by o-phenylene-derived amido phosphine ligands, N-(2-diphenylphosphinophenyl)-2,6-dimethylanilide ([Me-NP]-) and N-(2-diphenylphosphinophenyl)-2,6-diisopropylanilide ([iPr-NP]-), have been prepared. The reactions of trialkylaluminum with H[Me-NP] and H[iPr-NP], respectively, in refluxing toluene produced the corresponding dialkyl complexes [Me-NP]AlR(2) and [iPr-NP]AlR(2) (R = Me, Et). Deprotonation of H[Me-NP] with n-BuLi in THF at -35 degrees C followed by addition of AlCl(3) in toluene at -35 degrees C afforded [Me-NP]AlCl(2), which was subsequently reacted with 2 equiv of trimethylsilylmethyllithium in toluene to give [Me-NP]Al(CH(2)SiMe(3))(2). The aluminum complexes were all characterized by (1)H, (13)C, (31)P, and (27)Al NMR spectroscopy. The solid-state structures of monomeric, four-coordinate [Me-NP]AlEt(2) and [iPr-NP]AlMe(2) and five-coordinate [Me-NP]AlCl(2)(THF) were determined by X-ray crystallography. The (1)H NMR studies of [Me-NP]AlEt(2), [Me-NP]Al(CH(2)SiMe(3))(2), and [iPr-NP]AlEt(2) indicate diastereotopic alpha-hydrogen atoms in these molecules. Heteronuclear COSY and NOE experiments suggest that the phosphorus donor in [Me-NP]Al(CH(2)SiMe(3))(2) and [iPr-NP]AlEt(2) is coupled to only one of the diastereotopic alpha-hydrogen atoms that is virtually antiperiplanar with respect to the phosphorus atom.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Aluminum complexes with bidentate amido ligands: synthesis, structure and performance on ligand-initiated ring-opening polymerization of rac-lactide.

A series of mononuclear aluminum dimethyl complexes bearing bidentate N-[2-(1-piperidinyl)benzyl]anilino or N-(2-morpholinobenzyl)anilino ligands were synthesized via reactions of the corresponding proligands with trimethylaluminum upon heating, while at ambient temperature two trimethylaluminum adducts with neutral N-[2-(1-piperidinyl)benzyl]aniline proligands were obtained. These complexes we...

متن کامل

Nickel complexes incorporating an amido phosphine chelate with a pendant amine arm: synthesis, structure, and catalytic Kumada coupling.

A series of organonickel(II) complexes incorporating an amido phosphine ligand tethered with an amino pendant have been prepared and characterized. Deprotonation of N-(dimethylaminoethyl)-2-diphenylphosphinoaniline (H[PNN]) with one equivalent of n-BuLi in ethereal or hydrocarbon solutions at -35 °C generates cleanly dimeric {Li[PNN]}(2) as yellow crystals. The reaction of NiCl(2)(DME) with {Li...

متن کامل

Drastic effect of bidentate phosphine ligands on Pd-catalyzed hydroarylation of ethyl propiolate: a simple route to arylbutadienes.

Palladium complexes with bidentate phosphine ligands, Pd(dppe)(OAc)(2) and Pd(dppm)(OAc)(2), were found to be effective catalysts for reactions of simple arenes with ethyl propiolate, affording arylbutadiene derivatives selectively.

متن کامل

Synthesis of ferrocene-based amido-phosphine ligands via highly diastereoselective ortho-lithiation and their application in Pd-catalyzed asymmetric allylic alkylations

An efficient synthesis of novel planar chiral ferrocene-based amido-phosphine ligands was accomplished via highly diastereoselective ortho-lithiation and subsequent in situ trapping with chlorodiphenylphosphine. The palladium complexes of mono-phosphino ferrocenecarboxamide, bis-phosphino ferrocenedicarboxamide ligands, and analogues with a ferrocenophane framework were applied in the allylic a...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Inorganic chemistry

دوره 43 6  شماره 

صفحات  -

تاریخ انتشار 2004