Synthesis, Characterization, and Some Properties of Cp*W(NO)(H)(η3-allyl) Complexes

Baillie, R.; Holmes, A.; Lefèvre, G.; Patrick, B.; Shree, M.; Wakeham, R.; Legzdins, P.; Rosenfeld, D.; Wakeham, Russell

doi:10.1021/acs.inorgchem.5b00747

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**Synthesis, Characterization, and Some Properties of Cp*W(NO)(H)(η3-allyl) Complexes**

R. Baillie, A. Holmes, G. Lefèvre, B. Patrick, M. Shree, R. Wakeham, P. Legzdins, D. Rosenfeld, Russell Wakeham

Inorganic Chemistry, Volume: 54, Issue: 12, Pages: 5915 - 5929

Swansea University Author: Russell Wakeham

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DOI (Published version): 10.1021/acs.inorgchem.5b00747

Abstract

Sequential treatment at low temperatures of Cp*W(NO)Cl2 in THF with 1 equiv of a binary magnesium allyl reagent, followed by an excess of LiBH4, affords three new Cp*W(NO)(H)(η3-allyl) complexes, namely, Cp*W(NO)(H)(η3-CH2CHCMe2) (1), Cp*W(NO)(H)(η3-CH2CHCHPh) (2), and Cp*W(NO)(H)(η3-CH2CHCHMe) (3)....

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Published in:	Inorganic Chemistry
ISSN:	0020-1669 1520-510X
Published:	American Chemical Society (ACS) 2015
Online Access:	Check full text
URI:	https://cronfa.swan.ac.uk/Record/cronfa32710
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first_indexed	2017-03-27T12:57:28Z
last_indexed	2018-02-09T05:20:55Z
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spelling	2017-03-28T11:01:34.1295774 v2 32710 2017-03-27 Synthesis, Characterization, and Some Properties of CpW(NO)(H)(η3-allyl) Complexes 28c45bbeeba294da7042950705b98e0a 0000-0002-4304-0243 Russell Wakeham Russell Wakeham true false 2017-03-27 EEN Sequential treatment at low temperatures of CpW(NO)Cl2 in THF with 1 equiv of a binary magnesium allyl reagent, followed by an excess of LiBH4, affords three new CpW(NO)(H)(η3-allyl) complexes, namely, CpW(NO)(H)(η3-CH2CHCMe2) (1), CpW(NO)(H)(η3-CH2CHCHPh) (2), and CpW(NO)(H)(η3-CH2CHCHMe) (3). Complexes 1–3 are isolable as air-stable, analytically pure yellow solids in good to moderate yields by chromatography or fractional crystallization. In solutions, complex 1 exists as two coordination isomers in an 83:17 ratio differing with respect to the endo/exo orientation of the allyl ligand. In contrast, complexes 2 and 3 each exist as four coordination isomers, all differing by the orientation of their allyl ligands which can have either an endo or an exo orientation with the phenyl or methyl groups being either proximal or distal to the nitrosyl ligand. A DFT computational analysis using the major isomer of CpW(NO)(H)(η3-CH2CHCHMe) (3a) as the model complex has revealed that its lowest-energy thermal-decomposition pathway involves the intramolecular isomerization of 3a to the 16e η2-alkene complex, CpW(NO)(η2-CH2═CHCH2Me). Such η2-alkene complexes are isolable as their 18e PMe3 adducts when compounds 1–3 are thermolyzed in neat PMe3, the other organometallic products formed during these thermolyses being CpW(NO)(PMe3)2 (5) and, occasionally, CpW(NO)(H)(η1-allyl)(PMe3). 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 54 12 5915 5929 American Chemical Society (ACS) 0020-1669 1520-510X 30 6 2015 2015-06-30 10.1021/acs.inorgchem.5b00747 COLLEGE NANME Engineering COLLEGE CODE EEN Swansea University 2017-03-28T11:01:34.1295774 2017-03-27T11:03:24.6532842 Faculty of Science and Engineering School of Engineering and Applied Sciences - Uncategorised R. Baillie 1 A. Holmes 2 G. Lefèvre 3 B. Patrick 4 M. Shree 5 R. Wakeham 6 P. Legzdins 7 D. Rosenfeld 8 Russell Wakeham 0000-0002-4304-0243 9
title	Synthesis, Characterization, and Some Properties of Cp*W(NO)(H)(η3-allyl) Complexes
spellingShingle	Synthesis, Characterization, and Some Properties of Cp*W(NO)(H)(η3-allyl) Complexes Russell Wakeham
title_short	Synthesis, Characterization, and Some Properties of Cp*W(NO)(H)(η3-allyl) Complexes
title_full	Synthesis, Characterization, and Some Properties of Cp*W(NO)(H)(η3-allyl) Complexes
title_fullStr	Synthesis, Characterization, and Some Properties of Cp*W(NO)(H)(η3-allyl) Complexes
title_full_unstemmed	Synthesis, Characterization, and Some Properties of Cp*W(NO)(H)(η3-allyl) Complexes
title_sort	Synthesis, Characterization, and Some Properties of Cp*W(NO)(H)(η3-allyl) Complexes
author_id_str_mv	28c45bbeeba294da7042950705b98e0a
author_id_fullname_str_mv	28c45bbeeba294da7042950705b98e0a_***_Russell Wakeham
author	Russell Wakeham
author2	R. Baillie A. Holmes G. Lefèvre B. Patrick M. Shree R. Wakeham P. Legzdins D. Rosenfeld Russell Wakeham
format	Journal article
container_title	Inorganic Chemistry
container_volume	54
container_issue	12
container_start_page	5915
publishDate	2015
institution	Swansea University
issn	0020-1669 1520-510X
doi_str_mv	10.1021/acs.inorgchem.5b00747
publisher	American Chemical Society (ACS)
college_str	Faculty of Science and Engineering
hierarchytype
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
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description	Sequential treatment at low temperatures of CpW(NO)Cl2 in THF with 1 equiv of a binary magnesium allyl reagent, followed by an excess of LiBH4, affords three new CpW(NO)(H)(η3-allyl) complexes, namely, CpW(NO)(H)(η3-CH2CHCMe2) (1), CpW(NO)(H)(η3-CH2CHCHPh) (2), and CpW(NO)(H)(η3-CH2CHCHMe) (3). Complexes 1–3 are isolable as air-stable, analytically pure yellow solids in good to moderate yields by chromatography or fractional crystallization. In solutions, complex 1 exists as two coordination isomers in an 83:17 ratio differing with respect to the endo/exo orientation of the allyl ligand. In contrast, complexes 2 and 3 each exist as four coordination isomers, all differing by the orientation of their allyl ligands which can have either an endo or an exo orientation with the phenyl or methyl groups being either proximal or distal to the nitrosyl ligand. A DFT computational analysis using the major isomer of CpW(NO)(H)(η3-CH2CHCHMe) (3a) as the model complex has revealed that its lowest-energy thermal-decomposition pathway involves the intramolecular isomerization of 3a to the 16e η2-alkene complex, CpW(NO)(η2-CH2═CHCH2Me). Such η2-alkene complexes are isolable as their 18e PMe3 adducts when compounds 1–3 are thermolyzed in neat PMe3, the other organometallic products formed during these thermolyses being CpW(NO)(PMe3)2 (5) and, occasionally, Cp*W(NO)(H)(η1-allyl)(PMe3). 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	2015-06-30T03:40:11Z
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score	11.036334

Synthesis, Characterization, and Some Properties of Cp*W(NO)(H)(η3-allyl) Complexes

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