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Thioether complexes of WSCl4, WOCl4 and WSCl3 and evaluation of thiochloride complexes as CVD precursors for WS2 thin films

Thioether complexes of WSCl4, WOCl4 and WSCl3 and evaluation of thiochloride complexes as CVD precursors for WS2 thin films
Thioether complexes of WSCl4, WOCl4 and WSCl3 and evaluation of thiochloride complexes as CVD precursors for WS2 thin films
The red-brown [(WSCl4)2{µ-RS{CH2)2SR}] (R = Me, Ph, iPr) and [(WSCl4)2{µ-MeS{CH2)3SMe}] have been made by reaction of WSCl4 with the thioether in a 2:1 molar ratio, in anhydrous CH2Cl2 solution, and characterised by microanalysis, IR, UV/Vis and 1H NMR spectroscopy. The X-ray structures of the four dithioether complexes reveal square pyramidal WSCl4 units and bridging dithioethers with W=S trans to thioether sulfur. Paramagnetic W(V) complexes, [WSCl3{RS{CH2)2SR}] (R = Me, iPr), have been made similarly using a 1: ≥1 ratio of reactants or longer reaction times. The W(VI) complexes, [WSCl4(SMe2)] and [WSCl4(SeMe2)], are also described. Analogous complexes of WOCl4, [(WOCl4)2{RS(CH2)2SR}] (R = Ph, iPr), have been made similarly from WOCl4, but reactions using MeS(CH2)nSMe (n = 2, 3) led to reduction to W(V), forming [WOCl3{MeS{CH2)nSMe], both of which were identified crystallographically. Curiously, they are geometric isomers: [WOCl3{MeS(CH2)3SMe}] has the dithioether trans Cl/Cl whereas in [WOCl3{MeS(CH2)2SMe}] it is trans O/Cl. Remarkably, low pressure chemical vapour deposition (CVD) experiments using the dinuclear W(VI) species, [(WSCl4)2{iPrS(CH2)2SiPr}], as a single source precursor produced thin films of 4H-WS2, identified by grazing incidence X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy; the tungsten thiochloride complex is the first single source low pressure CVD precursor for WS2. In contrast, the mononuclear W(V) complex, [WSCl3{iPrS(CH2)2SiPr}], does not deposit WS2 under similar conditions.
0300-9246
2496-2504
Smith, Danielle, Emily
dca4b149-33c4-4bc6-9f67-3d46b862363c
Greenacre, Victoria
c665a38b-0b1a-4671-ac75-bf0679dd1c57
Hector, Andrew L.
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Robinson, Fred
8fc7b408-097f-4550-b189-5b6e3a49bf93
Thomas, Shibin
f9dd0751-582b-4c35-9725-36fbe08bbda8
Huang, Ruomeng
c6187811-ef2f-4437-8333-595c0d6ac978
Smith, Danielle, Emily
dca4b149-33c4-4bc6-9f67-3d46b862363c
Greenacre, Victoria
c665a38b-0b1a-4671-ac75-bf0679dd1c57
Hector, Andrew L.
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Robinson, Fred
8fc7b408-097f-4550-b189-5b6e3a49bf93
Thomas, Shibin
f9dd0751-582b-4c35-9725-36fbe08bbda8
Huang, Ruomeng
c6187811-ef2f-4437-8333-595c0d6ac978

Smith, Danielle, Emily, Greenacre, Victoria, Hector, Andrew L., Levason, William, Reid, Gillian, Robinson, Fred, Thomas, Shibin and Huang, Ruomeng (2020) Thioether complexes of WSCl4, WOCl4 and WSCl3 and evaluation of thiochloride complexes as CVD precursors for WS2 thin films. Dalton Transactions, 49 (8), 2496-2504. (doi:10.1039/D0DT00068J).

Record type: Article

Abstract

The red-brown [(WSCl4)2{µ-RS{CH2)2SR}] (R = Me, Ph, iPr) and [(WSCl4)2{µ-MeS{CH2)3SMe}] have been made by reaction of WSCl4 with the thioether in a 2:1 molar ratio, in anhydrous CH2Cl2 solution, and characterised by microanalysis, IR, UV/Vis and 1H NMR spectroscopy. The X-ray structures of the four dithioether complexes reveal square pyramidal WSCl4 units and bridging dithioethers with W=S trans to thioether sulfur. Paramagnetic W(V) complexes, [WSCl3{RS{CH2)2SR}] (R = Me, iPr), have been made similarly using a 1: ≥1 ratio of reactants or longer reaction times. The W(VI) complexes, [WSCl4(SMe2)] and [WSCl4(SeMe2)], are also described. Analogous complexes of WOCl4, [(WOCl4)2{RS(CH2)2SR}] (R = Ph, iPr), have been made similarly from WOCl4, but reactions using MeS(CH2)nSMe (n = 2, 3) led to reduction to W(V), forming [WOCl3{MeS{CH2)nSMe], both of which were identified crystallographically. Curiously, they are geometric isomers: [WOCl3{MeS(CH2)3SMe}] has the dithioether trans Cl/Cl whereas in [WOCl3{MeS(CH2)2SMe}] it is trans O/Cl. Remarkably, low pressure chemical vapour deposition (CVD) experiments using the dinuclear W(VI) species, [(WSCl4)2{iPrS(CH2)2SiPr}], as a single source precursor produced thin films of 4H-WS2, identified by grazing incidence X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy; the tungsten thiochloride complex is the first single source low pressure CVD precursor for WS2. In contrast, the mononuclear W(V) complex, [WSCl3{iPrS(CH2)2SiPr}], does not deposit WS2 under similar conditions.

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W(V)_and_W(VI)_thioether_chemistry_final revised_25_01_2020 - accepted - Accepted Manuscript
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Accepted/In Press date: 28 January 2020
e-pub ahead of print date: 28 January 2020
Published date: 28 February 2020

Identifiers

Local EPrints ID: 437587
URI: http://eprints.soton.ac.uk/id/eprint/437587
ISSN: 0300-9246
PURE UUID: 6a19ec01-ded7-473d-9927-4e46eaa4f673
ORCID for Danielle, Emily Smith: ORCID iD orcid.org/0000-0002-2446-1763
ORCID for Andrew L. Hector: ORCID iD orcid.org/0000-0002-9964-2163
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 06 Feb 2020 17:30
Last modified: 15 Sep 2021 04:13

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