Dimethylsilyl bis(amidinate)actinide complexes: Synthesis and reactivity towards oxygen containing substrates

TY - JOUR

T1 - Dimethylsilyl bis(amidinate)actinide complexes

T2 - Synthesis and reactivity towards oxygen containing substrates

AU - Karmel, Isabell S.R.

AU - Elkin, Tatyana

AU - Fridman, Natalia

AU - Eisen, Moris S.

PY - 2014/8/7

Y1 - 2014/8/7

N2 - The reactivity of the monoanionic amidinate ligand [(CH3) 3CNC(Ph)NSiMe2NC(Ph)-NHC(CH3)3]Li (1) with a silyl amido side arm towards the early actinides, uranium and thorium, was investigated. While the salt metathesis reaction with ThCl 4(thf)3 afforded the bis(amidinate)thorium(iv) dichloride complex [(CH3)3CNC(Ph)NSi(CH3) 2NC(Ph)-NHC(CH3)3]ThCl2 (2) in high yield, the reaction of ligand 1 with UCl4 leads to a Lewis acid supported nucleophilic attack of an incoming ligand unit, yielding the trichloro uranium complex [(CH3)3CNC(Ph)Si(CH3) 2-N(C(CH3)3)C(Ph)NSi(CH3) 2NC(Ph)N-(C(CH3)3]UCl3 (4). The exposure of in situ formed complex 2 to wet THF solutions (<1% w of water), gave the mono(amidinate)Th(iv)(chloro)(bis-hydroxo) dimeric complex [(CH 3)3CNC(Ph)NSiMe2NC(Ph)NHC(CH3) 3Th(OH)2(Cl)]2·(3) as bright red needles, exhibiting extremely short Th-OH bond distances (1.741(5) Å and 1.737(5) Å). The reactivity of the thorium complex 2 in the ring opening polymerization (ROP) was studied, showing high activity. Thermodynamic and kinetic measurements were performed to shed light on the mechanism for the ROP. This journal is

AB - The reactivity of the monoanionic amidinate ligand [(CH3) 3CNC(Ph)NSiMe2NC(Ph)-NHC(CH3)3]Li (1) with a silyl amido side arm towards the early actinides, uranium and thorium, was investigated. While the salt metathesis reaction with ThCl 4(thf)3 afforded the bis(amidinate)thorium(iv) dichloride complex [(CH3)3CNC(Ph)NSi(CH3) 2NC(Ph)-NHC(CH3)3]ThCl2 (2) in high yield, the reaction of ligand 1 with UCl4 leads to a Lewis acid supported nucleophilic attack of an incoming ligand unit, yielding the trichloro uranium complex [(CH3)3CNC(Ph)Si(CH3) 2-N(C(CH3)3)C(Ph)NSi(CH3) 2NC(Ph)N-(C(CH3)3]UCl3 (4). The exposure of in situ formed complex 2 to wet THF solutions (<1% w of water), gave the mono(amidinate)Th(iv)(chloro)(bis-hydroxo) dimeric complex [(CH 3)3CNC(Ph)NSiMe2NC(Ph)NHC(CH3) 3Th(OH)2(Cl)]2·(3) as bright red needles, exhibiting extremely short Th-OH bond distances (1.741(5) Å and 1.737(5) Å). The reactivity of the thorium complex 2 in the ring opening polymerization (ROP) was studied, showing high activity. Thermodynamic and kinetic measurements were performed to shed light on the mechanism for the ROP. This journal is

UR - http://www.scopus.com/inward/record.url?scp=84903840886&partnerID=8YFLogxK

U2 - 10.1039/c4dt01361a

DO - 10.1039/c4dt01361a

M3 - 文章

AN - SCOPUS:84903840886

SN - 1477-9226

VL - 43

SP - 11376

EP - 11387

JO - Dalton Transactions

JF - Dalton Transactions

IS - 29

ER -