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Cationic and Neutral Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C–H Activation

R. Rex, R. Wakeham, P. Brian, P. Legzdins, Russell Wakeham Orcid Logo

Inorganic Chemistry, Volume: 56, Issue: 6, Pages: 3612 - 3622

Swansea University Author: Russell Wakeham Orcid Logo

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DOI (Published version): 10.1021/acs.inorgchem.7b00027

Abstract

Treatment of CH2Cl2 solutions of Cp*M(NO)Cl2 (Cp* = η5-C5(CH3)5; M = Mo, W) first with 2 equiv of AgSbF6 in the presence of PhCN and then with 1 equiv of Ph2PCH2CH2PPh2 affords the yellow–orange salts [Cp*M(NO)(PhCN)(κ2-Ph2PCH2CH2PPh2)](SbF6)2 in good yields (M = Mo, W). Reduction of [Cp*M(NO)(PhCN)...

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Published in: Inorganic Chemistry
ISSN: 0020-1669 1520-510X
Published: American Chemical Society (ACS) 2017
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URI: https://cronfa.swan.ac.uk/Record/cronfa32716
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spelling 2017-06-19T15:15:07.6011497 v2 32716 2017-03-27 Cationic and Neutral Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C–H Activation 28c45bbeeba294da7042950705b98e0a 0000-0002-4304-0243 Russell Wakeham Russell Wakeham true false 2017-03-27 EEN Treatment of CH2Cl2 solutions of Cp*M(NO)Cl2 (Cp* = η5-C5(CH3)5; M = Mo, W) first with 2 equiv of AgSbF6 in the presence of PhCN and then with 1 equiv of Ph2PCH2CH2PPh2 affords the yellow–orange salts [Cp*M(NO)(PhCN)(κ2-Ph2PCH2CH2PPh2)](SbF6)2 in good yields (M = Mo, W). Reduction of [Cp*M(NO)(PhCN)(κ2-Ph2PCH2CH2PPh2)](SbF6)2 with 2 equiv of Cp2Co in C6H6 at 80 °C produces the corresponding 18e neutral compounds, Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) which have been isolated as analytically pure orange–red solids. The addition of 1 equiv of the Lewis acid, Sc(OTf)3, to solutions of Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) at room temperature results in the immediate formation of thermally stable Cp*M(NO→Sc(OTf)3)(H)(κ3-(C6H4)PhPCH2CH2PPh2) complexes in which one of the phenyl substituents of the Ph2PCH2CH2PPh2 ligands has undergone intramolecular orthometalation. In a similar manner, addition of BF3 produces the analogous Cp*M(NO→BF3)(H)(κ3-(C6H4)PhPCH2CH2PPh2) complexes. In contrast, B(C6F5)3 forms the 1:1 Lewis acid–base adducts, Cp*M(NO→B(C6F5)3)(κ2-Ph2PCH2CH2PPh2) in CH2Cl2 at room temperature. Upon warming to 80 °C, Cp*Mo(NO→B(C6F5)3)(κ2-Ph2PCH2CH2PPh2) converts cleanly to the orthometalated product Cp*Mo(NO→B(C6F5)3)(H)(κ3-(C6H4)PhPCH2CH2PPh2), but Cp*W(NO→B(C6F5)3)(κ2-Ph2PCH2CH2PPh2) generates a mixture of products whose identities remain to be ascertained. Attempts to extend this chemistry to include related Ph2PCH2PPh2 compounds have had only limited success. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses. Journal Article Inorganic Chemistry 56 6 3612 3622 American Chemical Society (ACS) 0020-1669 1520-510X 2 3 2017 2017-03-02 10.1021/acs.inorgchem.7b00027 COLLEGE NANME Engineering COLLEGE CODE EEN Swansea University 2017-06-19T15:15:07.6011497 2017-03-27T11:07:14.5529698 Faculty of Science and Engineering School of Engineering and Applied Sciences - Uncategorised R. Rex 1 R. Wakeham 2 P. Brian 3 P. Legzdins 4 Russell Wakeham 0000-0002-4304-0243 5 0032716-24042017112037.pdf handford2017.pdf 2017-04-24T11:20:37.6670000 Output 1275266 application/pdf Accepted Manuscript true 2018-03-02T00:00:00.0000000 true eng
title Cationic and Neutral Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C–H Activation
spellingShingle Cationic and Neutral Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C–H Activation
Russell Wakeham
title_short Cationic and Neutral Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C–H Activation
title_full Cationic and Neutral Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C–H Activation
title_fullStr Cationic and Neutral Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C–H Activation
title_full_unstemmed Cationic and Neutral Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C–H Activation
title_sort Cationic and Neutral Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C–H Activation
author_id_str_mv 28c45bbeeba294da7042950705b98e0a
author_id_fullname_str_mv 28c45bbeeba294da7042950705b98e0a_***_Russell Wakeham
author Russell Wakeham
author2 R. Rex
R. Wakeham
P. Brian
P. Legzdins
Russell Wakeham
format Journal article
container_title Inorganic Chemistry
container_volume 56
container_issue 6
container_start_page 3612
publishDate 2017
institution Swansea University
issn 0020-1669
1520-510X
doi_str_mv 10.1021/acs.inorgchem.7b00027
publisher American Chemical Society (ACS)
college_str Faculty of Science and Engineering
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hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Uncategorised{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Uncategorised
document_store_str 1
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description Treatment of CH2Cl2 solutions of Cp*M(NO)Cl2 (Cp* = η5-C5(CH3)5; M = Mo, W) first with 2 equiv of AgSbF6 in the presence of PhCN and then with 1 equiv of Ph2PCH2CH2PPh2 affords the yellow–orange salts [Cp*M(NO)(PhCN)(κ2-Ph2PCH2CH2PPh2)](SbF6)2 in good yields (M = Mo, W). Reduction of [Cp*M(NO)(PhCN)(κ2-Ph2PCH2CH2PPh2)](SbF6)2 with 2 equiv of Cp2Co in C6H6 at 80 °C produces the corresponding 18e neutral compounds, Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) which have been isolated as analytically pure orange–red solids. The addition of 1 equiv of the Lewis acid, Sc(OTf)3, to solutions of Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) at room temperature results in the immediate formation of thermally stable Cp*M(NO→Sc(OTf)3)(H)(κ3-(C6H4)PhPCH2CH2PPh2) complexes in which one of the phenyl substituents of the Ph2PCH2CH2PPh2 ligands has undergone intramolecular orthometalation. In a similar manner, addition of BF3 produces the analogous Cp*M(NO→BF3)(H)(κ3-(C6H4)PhPCH2CH2PPh2) complexes. In contrast, B(C6F5)3 forms the 1:1 Lewis acid–base adducts, Cp*M(NO→B(C6F5)3)(κ2-Ph2PCH2CH2PPh2) in CH2Cl2 at room temperature. Upon warming to 80 °C, Cp*Mo(NO→B(C6F5)3)(κ2-Ph2PCH2CH2PPh2) converts cleanly to the orthometalated product Cp*Mo(NO→B(C6F5)3)(H)(κ3-(C6H4)PhPCH2CH2PPh2), but Cp*W(NO→B(C6F5)3)(κ2-Ph2PCH2CH2PPh2) generates a mixture of products whose identities remain to be ascertained. Attempts to extend this chemistry to include related Ph2PCH2PPh2 compounds have had only limited success. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.
published_date 2017-03-02T03:40:11Z
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score 11.036334

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