Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR' Units (R = Ph2PNSiMe3; R' = CPh3): Alkali Metal-Mediated Push-Pull Effects with an Amido AuxiliaryCitation formats

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Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR' Units (R = Ph2PNSiMe3; R' = CPh3): Alkali Metal-Mediated Push-Pull Effects with an Amido Auxiliary. / Lu, Erli; Tuna, Floriana; Lewis, William; Kaltsoyannis, Nikolas; Liddle, Stephen.

In: Chemistry - A European Journal, Vol. 22, No. 33, 01.08.2016, p. 11554–11558 .

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@article{aa347eafd54b4581964884544f840212,
title = "Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR' Units (R = Ph2PNSiMe3; R' = CPh3): Alkali Metal-Mediated Push-Pull Effects with an Amido Auxiliary",
abstract = "We report uranium(IV)-carbene-imido-amide metalla-allene complexes [U(BIPMTMS)(NCPh3)(NHCPh3)(M)] (BIPMTMS = C(PPh2NSiMe3)2; M = Li or K) that can be described as R2C=U=NR' push-pull metalla-allene units, as organometallic counterparts of the well-known push-pull organic allenes. The solid state structures reveal that the R2C=U=NR' units adopt highly unusual cis-arrangements, which is also reproduced by gas-phase theoretical studies conducted without the alkali metals to remove their potential structure directing roles. Computational studies confirm the double-bond nature of the U=NR' and U=CR2 interactions, the latter increasingly attenuated by potassium then lithium when compared to the hypothetical alkali metal-free anion. Combined experimental and theoretical data show that the push-pull effect induced by the alkali metal cations and amide auxiliary gives a fundamental and tuneable structural influence over the C=UIV=N units.",
author = "Erli Lu and Floriana Tuna and William Lewis and Nikolas Kaltsoyannis and Stephen Liddle",
year = "2016",
month = "8",
day = "1",
doi = "10.1002/chem.201602603",
language = "English",
volume = "22",
pages = "11554–11558",
journal = "Chemistry: A European Journal",
issn = "0947-6539",
publisher = "John Wiley & Sons Ltd",
number = "33",

}

RIS

TY - JOUR

T1 - Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR' Units (R = Ph2PNSiMe3; R' = CPh3): Alkali Metal-Mediated Push-Pull Effects with an Amido Auxiliary

AU - Lu, Erli

AU - Tuna, Floriana

AU - Lewis, William

AU - Kaltsoyannis, Nikolas

AU - Liddle, Stephen

PY - 2016/8/1

Y1 - 2016/8/1

N2 - We report uranium(IV)-carbene-imido-amide metalla-allene complexes [U(BIPMTMS)(NCPh3)(NHCPh3)(M)] (BIPMTMS = C(PPh2NSiMe3)2; M = Li or K) that can be described as R2C=U=NR' push-pull metalla-allene units, as organometallic counterparts of the well-known push-pull organic allenes. The solid state structures reveal that the R2C=U=NR' units adopt highly unusual cis-arrangements, which is also reproduced by gas-phase theoretical studies conducted without the alkali metals to remove their potential structure directing roles. Computational studies confirm the double-bond nature of the U=NR' and U=CR2 interactions, the latter increasingly attenuated by potassium then lithium when compared to the hypothetical alkali metal-free anion. Combined experimental and theoretical data show that the push-pull effect induced by the alkali metal cations and amide auxiliary gives a fundamental and tuneable structural influence over the C=UIV=N units.

AB - We report uranium(IV)-carbene-imido-amide metalla-allene complexes [U(BIPMTMS)(NCPh3)(NHCPh3)(M)] (BIPMTMS = C(PPh2NSiMe3)2; M = Li or K) that can be described as R2C=U=NR' push-pull metalla-allene units, as organometallic counterparts of the well-known push-pull organic allenes. The solid state structures reveal that the R2C=U=NR' units adopt highly unusual cis-arrangements, which is also reproduced by gas-phase theoretical studies conducted without the alkali metals to remove their potential structure directing roles. Computational studies confirm the double-bond nature of the U=NR' and U=CR2 interactions, the latter increasingly attenuated by potassium then lithium when compared to the hypothetical alkali metal-free anion. Combined experimental and theoretical data show that the push-pull effect induced by the alkali metal cations and amide auxiliary gives a fundamental and tuneable structural influence over the C=UIV=N units.

U2 - 10.1002/chem.201602603

DO - 10.1002/chem.201602603

M3 - Article

VL - 22

SP - 11554

EP - 11558

JO - Chemistry: A European Journal

JF - Chemistry: A European Journal

SN - 0947-6539

IS - 33

ER -