Bis(alkyl) rare-earth complexes supported by a new tridentate amidinate ligand with a pendant diphenylphosphine oxide group. Synthesis, structures and catalytic activity in isoprene polymerization.

@article{Tolpygin2015BisalkylRC,
  title={Bis(alkyl) rare-earth complexes supported by a new tridentate amidinate ligand with a pendant diphenylphosphine oxide group. Synthesis, structures and catalytic activity in isoprene polymerization.},
  author={Aleksei O. Tolpygin and Tatyana A. Glukhova and Anton V. Cherkasov and Georgy K. Fukin and Diana V. Aleksanyan and Dongmei Cui and Alexander A. Trifonov},
  journal={Dalton transactions},
  year={2015},
  volume={44 37},
  pages={
          16465-74
        }
}
A new tridentate amidine 2-[Ph2P(O)]C6H4NHC(tBu)[double bond, length as m-dash]N(2,6-Me2C6H3) (1) bearing a side chain pendant Ph2P[double bond, length as m-dash]O group was synthesized and proved to be a suitable ligand for coordination to rare-earths ions. Bis(alkyl) complexes {2-[Ph2P(O)]C6H4NC(tBu)N(2,6-Me2C6H3)}Ln(CH2SiMe3)2(THF)n (Ln = Y, n = 1 (3), Ln = Er, n = 1 (4), Ln = Lu, n = 0 (5)) were prepared using alkane elimination reactions of and Ln(CH2SiMe3)3(THF)2 (Ln = Y, Er, Lu) in… 
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Bis(amido) rare-earth complexes coordinated by tridentate amidinate ligand: synthesis, structure and catalytic activity in the polymerization of isoprene and rac-lactide
A series of bis(amido) complexes of rare earth metals {2-[Ph2P(O)]C6H4NC(tBu)N(2,6-Me2C6H3)}Ln(N(SiMe3)2)2, (Ln = Y (2), Nd (3), La (4)) was synthesized using the amine elimination reaction of…
Bis(alkyl) rare-earth complexes coordinated by bulky tridentate amidinate ligands bearing pendant Ph2P[double bond, length as m-dash]O and Ph2P[double bond, length as m-dash]NR groups. Synthesis, structures and catalytic activity in stereospecific isoprene polymerization.
TLDR
The bis(alkyl) complexes coordinated by tridentate amidinate ligands containing different pendant donor groups proved to be active in isoprene polymerization and enable complete conversion of 1000-10 000 equivalents of the monomer into a polymer at 25 °C within 0.5-24 h affording polyisoprenes with polydispersities Mw/Mn.
Chromium complexes bearing amidinato-phosphino ligand: synthesis, characterization, and catalytic properties of ethylene tri-/tetramerization and polymerization.
TLDR
Upon activation with an organoaluminum cocatalyst, complexes 4-6 were all catalytically active in ethylene tri-/tetramerization along with ethylene polymerization, and complexes 7-11 functioned as well but in ethane polymerization.
Amido Ln(II) Complexes Coordinated by Bi- and Tridentate Amidinate Ligands: Nonconventional Coordination Modes of Amidinate Ligands and Catalytic Activity in Intermolecular Hydrophosphination of Styrenes and Tolane.
TLDR
Application of tridentate amidinate ligand allowed one to increase catalytic activity significantly: for 2Sm TOF was found to be 8.3 h(-1), and for the addition of PhPH2 to para-substituted styrenes catalyzed by 2Sm it was found that electron-withdrawing substituents do not affect the reaction rate while electron-donating groups noticeably slow down the reaction.
Selective Intermolecular C–H Bond Activation: A Straightforward Synthetic Approach to Heteroalkyl Yttrium Complexes Containing a Bis(pyrazolyl)methyl Ligand
The reactions of bis(pyrazolyl)methanes CH2(C3HN2R2-3,5)2 (R = Me, tBu) with Y(CH2SiMe3)3(THF)2 and LY(CH2SiMe3)2(THF)n (L = amidopyridinate (Ap′), amidinate (Amd), tridentate amidinate bearing…
Neodymium dihalide complexes with a tridentate amidinate phosphine oxide ligand: synthesis, structure, and catalytic activity in isoprene polymerization
The deprotonation of amidine 2-[Ph2P(O)]C6H4NHC(But)=N(2,6-Me2C6H3) (1) with BunLi affords lithium amidinate {2-[Ph2P(O)]C6H4NLiC(But)=N(2,6-Me2C6H3)}2 (2) having a dimeric structure, as demonstrated…
Lutetium and yttrium complexes supported by an anilido-oxazoline ligand for polymerization of 1,3-conjugated dienes and ε-caprolactone
Lutetium and yttrium dialkyl complexes supported by an anilido-oxazoline ligand were synthesized, and their catalytic behaviors toward polymerization of isoprene (IP), β-myrcene (Myr) and…
(Amido)‐ and (Chlorido)titanium and ‐zirconium Complexes Coordinated by ansa‐Bis(amidinate) Ligands with a Rigid o‐Phenylene Linker
Bis-amido and bis-chlorine TiIV and ZrIV complexes stabilized by ansa bis(amidinate) ligands were prepared in fairly good yields by reacting a (bis)amidine ligand [C6H4-1,2-{NC(tBu)N(2,6-R2C6H3)H}2…
Neodymium monochloride and monoallyl complexes {2-[Ph2P(O)]C6H4NC(But)N(2,6-Me2C6H3)}2NdR (R = Cl, CH2CH=CH2) with the tridentate amidinate ligand in the catalysis of ring-opening polymerization of cyclic esters
The reaction of tridentate amidine 2-[Ph2P(O)]C6H4NHC(But)=N(2,6-Me2C6H3) (1) containing the side-chain donor group Ph2P=O with NdCl[N(SiMe3)2]2 (2) in a molar ratio of2:1 afforded the neodymium…
Regio- and stereo-selective polymerization of 1,3-butadiene catalyzed by phosphorus-nitrogen PN3-pincer cobalt(ii) complexes.
TLDR
The polymerization results show that the cis-1,4 selectivity is influenced by the steric hindrance, increasing with the bulkiness of the substituent groups at the 3,5-positions of the pyrazole moiety, together with a slight decrease in activity.
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TLDR
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Thiophene-NPN Ligand Supported Rare-Earth Metal Bis(alkyl) Complexes. Synthesis and Catalysis toward Highly trans-1,4 Selective Polymerization of Butadiene
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TLDR
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TLDR
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NNN-Tridentate Pyrrolyl Rare-Earth Metal Complexes: Structure and Catalysis on Specific Selective Living Polymerization of Isoprene
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