Structural Tungsten-Imido Chemistry: The Gas-Phase Structure of W(NBut)2(NHBut)2 and the Solid-State Structures of Novel Heterobimetallic W/N/M (M = Rh, Pd, Zn) Species

Hamid Choujaa; Samuel D. Cosham; Andrew L. Johnson; Graeme R. Kafka; Mary F. Mahon; Sarah L. Masters; Kieran C. Molloy; David W. H. Rankin; Heather E. Robertson; Derek A. Wann

doi:10.1021/ic8021134

Structural Tungsten-Imido Chemistry: The Gas-Phase Structure of W(NBu^{t)₂(NHBu^t)₂ and the Solid-State Structures of Novel Heterobimetallic W/N/M (M = Rh, Pd, Zn) Species}

Hamid Choujaa, Samuel D. Cosham, Andrew L. Johnson, Graeme R. Kafka, Mary F. Mahon, Sarah L. Masters, Kieran C. Molloy, David W. H. Rankin, Heather E. Robertson, Derek A. Wann

Research output: Contribution to journal › Article › peer-review

Abstract

The gas-phase (electron diffraction) and solid-state (X-ray) structures of W(NBu^t)₂(NHBu^t)₂ (1) have been determined. In the gas phase, 1 adopts both C₁ and C₂ conformations in a 69:31 ratio. The solid-state structure is disordered over two equal sites, both showing approximate C₂ conformation as in the gas phase; the imido and amido centers are, however, clearly distinguished. Compound 1 has been used to synthesize novel heterobimetallic derivatives. W(NBu^t)₄[Rh(COD)]₂ (3) and W(NBu^t)₄[Pd(η³-C₃H₅)]₂ (4) via the dilithiated intermediate Li₂[W(NBu^t)₄] (2). In both cases, the [W(NBu^t)₄] moiety bridges the two organometallic fragments. Reaction of 1 with Me₂Zn has produced [Me(Bu^tN))W(μ-NBu^t)₂ZnMe(NH₂Bu^t)] (5). The structures of 3, 4, and 5 have been determined. Thermal decomposition of 4 under an autogenerated pressure at 700 °C has formed the hitherto uncharacterized bimetallic alloy WPd₂.

Original language	English
Pages (from-to)	2289-2299
Number of pages	11
Journal	Inorganic Chemistry
Volume	48
Issue number	5
DOIs	https://doi.org/10.1021/ic8021134
Publication status	Published - 2 Mar 2009

Keywords

CHEMICAL-VAPOR-DEPOSITION
ATOMIC LAYER DEPOSITION
RAY CRYSTAL-STRUCTURES
ELECTRON-DIFFRACTION
MOLECULAR-STRUCTURE
THIN-FILMS
ELEVATED-TEMPERATURE
AUTOGENIC PRESSURE
TRANSITION-METALS
AB-INITIO

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10.1021/ic8021134

http://pubs.acs.org/doi/abs/10.1021/ic8021134

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Choujaa, H., Cosham, S. D., Johnson, A. L., Kafka, G. R., Mahon, M. F., Masters, S. L., Molloy, K. C., Rankin, D. W. H., Robertson, H. E., & Wann, D. A. (2009). Structural Tungsten-Imido Chemistry: The Gas-Phase Structure of W(NBu^{t)₂(NHBu^t)₂ and the Solid-State Structures of Novel Heterobimetallic W/N/M (M = Rh, Pd, Zn) Species}. Inorganic Chemistry, 48(5), 2289-2299. https://doi.org/10.1021/ic8021134

Choujaa, Hamid ; Cosham, Samuel D. ; Johnson, Andrew L. ; Kafka, Graeme R. ; Mahon, Mary F. ; Masters, Sarah L. ; Molloy, Kieran C. ; Rankin, David W. H. ; Robertson, Heather E. ; Wann, Derek A. / Structural Tungsten-Imido Chemistry: The Gas-Phase Structure of W(NBu^{t)₂(NHBu^t)₂ and the Solid-State Structures of Novel Heterobimetallic W/N/M (M = Rh, Pd, Zn) Species}. In: Inorganic Chemistry. 2009 ; Vol. 48, No. 5. pp. 2289-2299.

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title = "Structural Tungsten-Imido Chemistry: The Gas-Phase Structure of W(NBut)2(NHBut)2 and the Solid-State Structures of Novel Heterobimetallic W/N/M (M = Rh, Pd, Zn) Species",

abstract = "The gas-phase (electron diffraction) and solid-state (X-ray) structures of W(NBut)2(NHBut)2 (1) have been determined. In the gas phase, 1 adopts both C1 and C2 conformations in a 69:31 ratio. The solid-state structure is disordered over two equal sites, both showing approximate C2 conformation as in the gas phase; the imido and amido centers are, however, clearly distinguished. Compound 1 has been used to synthesize novel heterobimetallic derivatives. W(NBut)4[Rh(COD)]2 (3) and W(NBut)4[Pd(η3-C3H5)]2 (4) via the dilithiated intermediate Li2[W(NBut)4] (2). In both cases, the [W(NBut)4] moiety bridges the two organometallic fragments. Reaction of 1 with Me2Zn has produced [Me(ButN))W(μ-NBut)2ZnMe(NH2But)] (5). The structures of 3, 4, and 5 have been determined. Thermal decomposition of 4 under an autogenerated pressure at 700 °C has formed the hitherto uncharacterized bimetallic alloy WPd2.",

keywords = "CHEMICAL-VAPOR-DEPOSITION, ATOMIC LAYER DEPOSITION, RAY CRYSTAL-STRUCTURES, ELECTRON-DIFFRACTION, MOLECULAR-STRUCTURE, THIN-FILMS, ELEVATED-TEMPERATURE, AUTOGENIC PRESSURE, TRANSITION-METALS, AB-INITIO",

author = "Hamid Choujaa and Cosham, {Samuel D.} and Johnson, {Andrew L.} and Kafka, {Graeme R.} and Mahon, {Mary F.} and Masters, {Sarah L.} and Molloy, {Kieran C.} and Rankin, {David W. H.} and Robertson, {Heather E.} and Wann, {Derek A.}",

year = "2009",

month = mar,

day = "2",

doi = "10.1021/ic8021134",

language = "English",

volume = "48",

pages = "2289--2299",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "5",

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Choujaa, H, Cosham, SD, Johnson, AL, Kafka, GR, Mahon, MF, Masters, SL, Molloy, KC, Rankin, DWH, Robertson, HE & Wann, DA 2009, 'Structural Tungsten-Imido Chemistry: The Gas-Phase Structure of W(NBu^{t)₂(NHBu^t)₂ and the Solid-State Structures of Novel Heterobimetallic W/N/M (M = Rh, Pd, Zn) Species}', Inorganic Chemistry, vol. 48, no. 5, pp. 2289-2299. https://doi.org/10.1021/ic8021134

Structural Tungsten-Imido Chemistry: The Gas-Phase Structure of W(NBu^{t)₂(NHBu^t)₂ and the Solid-State Structures of Novel Heterobimetallic W/N/M (M = Rh, Pd, Zn) Species}. / Choujaa, Hamid; Cosham, Samuel D.; Johnson, Andrew L.; Kafka, Graeme R.; Mahon, Mary F.; Masters, Sarah L.; Molloy, Kieran C.; Rankin, David W. H.; Robertson, Heather E.; Wann, Derek A.

In: Inorganic Chemistry, Vol. 48, No. 5, 02.03.2009, p. 2289-2299.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Structural Tungsten-Imido Chemistry: The Gas-Phase Structure of W(NBut)2(NHBut)2 and the Solid-State Structures of Novel Heterobimetallic W/N/M (M = Rh, Pd, Zn) Species

AU - Choujaa, Hamid

AU - Cosham, Samuel D.

AU - Johnson, Andrew L.

AU - Kafka, Graeme R.

AU - Mahon, Mary F.

AU - Masters, Sarah L.

AU - Molloy, Kieran C.

AU - Rankin, David W. H.

AU - Robertson, Heather E.

AU - Wann, Derek A.

PY - 2009/3/2

Y1 - 2009/3/2

N2 - The gas-phase (electron diffraction) and solid-state (X-ray) structures of W(NBut)2(NHBut)2 (1) have been determined. In the gas phase, 1 adopts both C1 and C2 conformations in a 69:31 ratio. The solid-state structure is disordered over two equal sites, both showing approximate C2 conformation as in the gas phase; the imido and amido centers are, however, clearly distinguished. Compound 1 has been used to synthesize novel heterobimetallic derivatives. W(NBut)4[Rh(COD)]2 (3) and W(NBut)4[Pd(η3-C3H5)]2 (4) via the dilithiated intermediate Li2[W(NBut)4] (2). In both cases, the [W(NBut)4] moiety bridges the two organometallic fragments. Reaction of 1 with Me2Zn has produced [Me(ButN))W(μ-NBut)2ZnMe(NH2But)] (5). The structures of 3, 4, and 5 have been determined. Thermal decomposition of 4 under an autogenerated pressure at 700 °C has formed the hitherto uncharacterized bimetallic alloy WPd2.

AB - The gas-phase (electron diffraction) and solid-state (X-ray) structures of W(NBut)2(NHBut)2 (1) have been determined. In the gas phase, 1 adopts both C1 and C2 conformations in a 69:31 ratio. The solid-state structure is disordered over two equal sites, both showing approximate C2 conformation as in the gas phase; the imido and amido centers are, however, clearly distinguished. Compound 1 has been used to synthesize novel heterobimetallic derivatives. W(NBut)4[Rh(COD)]2 (3) and W(NBut)4[Pd(η3-C3H5)]2 (4) via the dilithiated intermediate Li2[W(NBut)4] (2). In both cases, the [W(NBut)4] moiety bridges the two organometallic fragments. Reaction of 1 with Me2Zn has produced [Me(ButN))W(μ-NBut)2ZnMe(NH2But)] (5). The structures of 3, 4, and 5 have been determined. Thermal decomposition of 4 under an autogenerated pressure at 700 °C has formed the hitherto uncharacterized bimetallic alloy WPd2.

KW - CHEMICAL-VAPOR-DEPOSITION

KW - ATOMIC LAYER DEPOSITION

KW - RAY CRYSTAL-STRUCTURES

KW - ELECTRON-DIFFRACTION

KW - MOLECULAR-STRUCTURE

KW - THIN-FILMS

KW - ELEVATED-TEMPERATURE

KW - AUTOGENIC PRESSURE

KW - TRANSITION-METALS

KW - AB-INITIO

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U2 - 10.1021/ic8021134

DO - 10.1021/ic8021134

M3 - Article

VL - 48

SP - 2289

EP - 2299

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 5

ER -

Structural Tungsten-Imido Chemistry: The Gas-Phase Structure of W(NBu^{t)₂(NHBu^t)₂ and the Solid-State Structures of Novel Heterobimetallic W/N/M (M = Rh, Pd, Zn) Species}

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