Lanthanide tri-benzyl complexes: Structural variations and useful precursors to phosphorus-stabilised lanthanide carbenesCitation formats

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Lanthanide tri-benzyl complexes: Structural variations and useful precursors to phosphorus-stabilised lanthanide carbenes. / Wooles, Ashley J.; Mills, David P.; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

In: Dalton Transactions, Vol. 39, No. 2, 2010, p. 500-510.

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Wooles, Ashley J. ; Mills, David P. ; Lewis, William ; Blake, Alexander J. ; Liddle, Stephen T. / Lanthanide tri-benzyl complexes: Structural variations and useful precursors to phosphorus-stabilised lanthanide carbenes. In: Dalton Transactions. 2010 ; Vol. 39, No. 2. pp. 500-510.

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@article{3054860a0b314716ab899a006996ffca,
title = "Lanthanide tri-benzyl complexes: Structural variations and useful precursors to phosphorus-stabilised lanthanide carbenes",
abstract = "Reaction of [Ln(I)3(THF)4] (Ln = Ce, Pr) or [Ln(I)3(THF)3.5] (Ln = Nd, Sm, Gd, Dy, Er) with three equivalents of [KBz] (Bz = CH2C6H5) at 0 °C afforded the corresponding lanthanide tri-benzyl complexes [Ln(Bz) 3(THF)3] [Ln = Ce (2), Pr (3), Nd (4), Sm (5), Gd (6), Dy (7), Er (8) La (11)] in 48-75{\%} crystalline yields, with the exception of the redox active samarium complex, which was isolated in poor (20{\%}) yield. Complexes 2-8 were found to adopt distorted octahedral geometries, where the Bz and THF groups are bound in a mutually fac manner in the solid state. Although the series is structurally similar, classification of three structural types can be made on the basis of the lanthanide contraction: (i) complexes which exhibit three η2 Ln⋯Cipso contacts (1-4, 11); (ii) complexes which show one η2 Ln⋯Cipso contact (5); (iii) complexes with no multi-hapto interactions (6-8). For ytterbium, the mixed valence, YbII/YbIII complex [YbII(Bz) (THF)5]+[YbIII(Bz)4(THF) 2]- (9) was reproducibly formed at 0 °C and -78 °C as a result of partial (50{\%}) YbIII→ YbII reduction with concomitant formation of half an equivalent of 1,2-diphenylethane by oxidative coupling. Tri-valent [Yb(Bz)3(THF)3] (10) was apparently not formed. The synthetic utility of tri-benzyl lanthanide complexes 2-8 and 11 were tested in reactions with the bis-(iminophosphorano)methane H2C(PPh2NSiMe3)2 (H 2-BIPM), which afforded [Ln(BIPM)(H-BIPM)] [Ln = La (12), Ce (13), Pr (14), Nd (15), Sm (16), Gd (17)] and [Ln(BIPM)(Bz)(THF)] [Ln = Dy (18), Er (19)]. Compounds 2-9 and 12-19 have been variously characterised by X-ray crystallography, multi-nuclear NMR spectroscopy, FTIR spectroscopy, room temperature Evans method solution magnetic moments and CHN micro-analyses. {\circledC} The Royal Society of Chemistry.",
author = "Wooles, {Ashley J.} and Mills, {David P.} and William Lewis and Blake, {Alexander J.} and Liddle, {Stephen T.}",
year = "2010",
doi = "10.1039/b911717b",
language = "English",
volume = "39",
pages = "500--510",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "2",

}

RIS

TY - JOUR

T1 - Lanthanide tri-benzyl complexes: Structural variations and useful precursors to phosphorus-stabilised lanthanide carbenes

AU - Wooles, Ashley J.

AU - Mills, David P.

AU - Lewis, William

AU - Blake, Alexander J.

AU - Liddle, Stephen T.

PY - 2010

Y1 - 2010

N2 - Reaction of [Ln(I)3(THF)4] (Ln = Ce, Pr) or [Ln(I)3(THF)3.5] (Ln = Nd, Sm, Gd, Dy, Er) with three equivalents of [KBz] (Bz = CH2C6H5) at 0 °C afforded the corresponding lanthanide tri-benzyl complexes [Ln(Bz) 3(THF)3] [Ln = Ce (2), Pr (3), Nd (4), Sm (5), Gd (6), Dy (7), Er (8) La (11)] in 48-75% crystalline yields, with the exception of the redox active samarium complex, which was isolated in poor (20%) yield. Complexes 2-8 were found to adopt distorted octahedral geometries, where the Bz and THF groups are bound in a mutually fac manner in the solid state. Although the series is structurally similar, classification of three structural types can be made on the basis of the lanthanide contraction: (i) complexes which exhibit three η2 Ln⋯Cipso contacts (1-4, 11); (ii) complexes which show one η2 Ln⋯Cipso contact (5); (iii) complexes with no multi-hapto interactions (6-8). For ytterbium, the mixed valence, YbII/YbIII complex [YbII(Bz) (THF)5]+[YbIII(Bz)4(THF) 2]- (9) was reproducibly formed at 0 °C and -78 °C as a result of partial (50%) YbIII→ YbII reduction with concomitant formation of half an equivalent of 1,2-diphenylethane by oxidative coupling. Tri-valent [Yb(Bz)3(THF)3] (10) was apparently not formed. The synthetic utility of tri-benzyl lanthanide complexes 2-8 and 11 were tested in reactions with the bis-(iminophosphorano)methane H2C(PPh2NSiMe3)2 (H 2-BIPM), which afforded [Ln(BIPM)(H-BIPM)] [Ln = La (12), Ce (13), Pr (14), Nd (15), Sm (16), Gd (17)] and [Ln(BIPM)(Bz)(THF)] [Ln = Dy (18), Er (19)]. Compounds 2-9 and 12-19 have been variously characterised by X-ray crystallography, multi-nuclear NMR spectroscopy, FTIR spectroscopy, room temperature Evans method solution magnetic moments and CHN micro-analyses. © The Royal Society of Chemistry.

AB - Reaction of [Ln(I)3(THF)4] (Ln = Ce, Pr) or [Ln(I)3(THF)3.5] (Ln = Nd, Sm, Gd, Dy, Er) with three equivalents of [KBz] (Bz = CH2C6H5) at 0 °C afforded the corresponding lanthanide tri-benzyl complexes [Ln(Bz) 3(THF)3] [Ln = Ce (2), Pr (3), Nd (4), Sm (5), Gd (6), Dy (7), Er (8) La (11)] in 48-75% crystalline yields, with the exception of the redox active samarium complex, which was isolated in poor (20%) yield. Complexes 2-8 were found to adopt distorted octahedral geometries, where the Bz and THF groups are bound in a mutually fac manner in the solid state. Although the series is structurally similar, classification of three structural types can be made on the basis of the lanthanide contraction: (i) complexes which exhibit three η2 Ln⋯Cipso contacts (1-4, 11); (ii) complexes which show one η2 Ln⋯Cipso contact (5); (iii) complexes with no multi-hapto interactions (6-8). For ytterbium, the mixed valence, YbII/YbIII complex [YbII(Bz) (THF)5]+[YbIII(Bz)4(THF) 2]- (9) was reproducibly formed at 0 °C and -78 °C as a result of partial (50%) YbIII→ YbII reduction with concomitant formation of half an equivalent of 1,2-diphenylethane by oxidative coupling. Tri-valent [Yb(Bz)3(THF)3] (10) was apparently not formed. The synthetic utility of tri-benzyl lanthanide complexes 2-8 and 11 were tested in reactions with the bis-(iminophosphorano)methane H2C(PPh2NSiMe3)2 (H 2-BIPM), which afforded [Ln(BIPM)(H-BIPM)] [Ln = La (12), Ce (13), Pr (14), Nd (15), Sm (16), Gd (17)] and [Ln(BIPM)(Bz)(THF)] [Ln = Dy (18), Er (19)]. Compounds 2-9 and 12-19 have been variously characterised by X-ray crystallography, multi-nuclear NMR spectroscopy, FTIR spectroscopy, room temperature Evans method solution magnetic moments and CHN micro-analyses. © The Royal Society of Chemistry.

U2 - 10.1039/b911717b

DO - 10.1039/b911717b

M3 - Article

VL - 39

SP - 500

EP - 510

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 2

ER -