Coordinatively Unsaturated W(IV)−Bis(pyridine) Complexes, a Reactive Source of W(IV)

Addition of 2 equiv of a σ-donor ligand (L = pyridine, 4-picoline, or quinoline) to complexes of the type [W(NPh)(η4-arene)(o-(Me3SiN)2C6H4)] (arene = CH3CH2C6H5 (3), CH3CH2CH2C6H5 (4)) gave the W(IV)L2 compounds, [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)2] (5), [W(NPh)(o-(Me3SiN)2C6H4)(p−C6H7N)2] (6), and [W...

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Published in:Inorganic chemistry 2001-09, Vol.40 (20), p.5077-5082
Main Authors: Mills, R. C, Wang, S. Y. S, Abboud, K. A, Boncella, J. M
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container_title Inorganic chemistry
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creator Mills, R. C
Wang, S. Y. S
Abboud, K. A
Boncella, J. M
description Addition of 2 equiv of a σ-donor ligand (L = pyridine, 4-picoline, or quinoline) to complexes of the type [W(NPh)(η4-arene)(o-(Me3SiN)2C6H4)] (arene = CH3CH2C6H5 (3), CH3CH2CH2C6H5 (4)) gave the W(IV)L2 compounds, [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)2] (5), [W(NPh)(o-(Me3SiN)2C6H4)(p−C6H7N)2] (6), and [W(NPh)(o-(Me3SiN)2C6H4)(C9H7N)2] (7). Synthesis of compounds 5 and 6 by Na° reduction of [W(NPh)(o-(Me3SiN)2C6H4)Cl2] in the presence of 3 equiv of L (L = 5, pyridine or 6, 4-picoline) is also presented. Compounds 5, 6, and 7 display hindered rotation of the donor ligands about the W−N bonds, resulting from a steric interaction with the Me3Si groups of the diamide ligand. The coordinative unsaturation of 5 and 6 has also been explored. Compounds 5 and 6 readily react with either CO and PMe3 to generated the six coordinate complexes [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)2(CO)] (8a), [W(NPh)(o-(Me3SiN)2C6H4)(C6H7N)2(CO)] (8b), [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)(PMe3)2] (10a), and [W(NPh)(o-(Me3SiN)2C6H4)(C6H7N)(PMe3)2] (10b), respectively.
doi_str_mv 10.1021/ic010195r
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C ; Wang, S. Y. S ; Abboud, K. A ; Boncella, J. M</creator><creatorcontrib>Mills, R. C ; Wang, S. Y. S ; Abboud, K. A ; Boncella, J. M</creatorcontrib><description>Addition of 2 equiv of a σ-donor ligand (L = pyridine, 4-picoline, or quinoline) to complexes of the type [W(NPh)(η4-arene)(o-(Me3SiN)2C6H4)] (arene = CH3CH2C6H5 (3), CH3CH2CH2C6H5 (4)) gave the W(IV)L2 compounds, [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)2] (5), [W(NPh)(o-(Me3SiN)2C6H4)(p−C6H7N)2] (6), and [W(NPh)(o-(Me3SiN)2C6H4)(C9H7N)2] (7). Synthesis of compounds 5 and 6 by Na° reduction of [W(NPh)(o-(Me3SiN)2C6H4)Cl2] in the presence of 3 equiv of L (L = 5, pyridine or 6, 4-picoline) is also presented. Compounds 5, 6, and 7 display hindered rotation of the donor ligands about the W−N bonds, resulting from a steric interaction with the Me3Si groups of the diamide ligand. The coordinative unsaturation of 5 and 6 has also been explored. Compounds 5 and 6 readily react with either CO and PMe3 to generated the six coordinate complexes [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)2(CO)] (8a), [W(NPh)(o-(Me3SiN)2C6H4)(C6H7N)2(CO)] (8b), [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)(PMe3)2] (10a), and [W(NPh)(o-(Me3SiN)2C6H4)(C6H7N)(PMe3)2] (10b), respectively.</description><identifier>ISSN: 0020-1669</identifier><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/ic010195r</identifier><identifier>PMID: 11559063</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>Inorganic chemistry, 2001-09, Vol.40 (20), p.5077-5082</ispartof><rights>Copyright © 2001 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a349t-e19a93713143d1291d6813dde91d5059fe62926c623a883bd1027d50c7ddca023</citedby><cites>FETCH-LOGICAL-a349t-e19a93713143d1291d6813dde91d5059fe62926c623a883bd1027d50c7ddca023</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/11559063$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Mills, R. C</creatorcontrib><creatorcontrib>Wang, S. Y. S</creatorcontrib><creatorcontrib>Abboud, K. A</creatorcontrib><creatorcontrib>Boncella, J. M</creatorcontrib><title>Coordinatively Unsaturated W(IV)−Bis(pyridine) Complexes, a Reactive Source of W(IV)</title><title>Inorganic chemistry</title><addtitle>Inorg. Chem</addtitle><description>Addition of 2 equiv of a σ-donor ligand (L = pyridine, 4-picoline, or quinoline) to complexes of the type [W(NPh)(η4-arene)(o-(Me3SiN)2C6H4)] (arene = CH3CH2C6H5 (3), CH3CH2CH2C6H5 (4)) gave the W(IV)L2 compounds, [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)2] (5), [W(NPh)(o-(Me3SiN)2C6H4)(p−C6H7N)2] (6), and [W(NPh)(o-(Me3SiN)2C6H4)(C9H7N)2] (7). Synthesis of compounds 5 and 6 by Na° reduction of [W(NPh)(o-(Me3SiN)2C6H4)Cl2] in the presence of 3 equiv of L (L = 5, pyridine or 6, 4-picoline) is also presented. Compounds 5, 6, and 7 display hindered rotation of the donor ligands about the W−N bonds, resulting from a steric interaction with the Me3Si groups of the diamide ligand. The coordinative unsaturation of 5 and 6 has also been explored. Compounds 5 and 6 readily react with either CO and PMe3 to generated the six coordinate complexes [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)2(CO)] (8a), [W(NPh)(o-(Me3SiN)2C6H4)(C6H7N)2(CO)] (8b), [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)(PMe3)2] (10a), and [W(NPh)(o-(Me3SiN)2C6H4)(C6H7N)(PMe3)2] (10b), respectively.</description><issn>0020-1669</issn><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2001</creationdate><recordtype>article</recordtype><recordid>eNptkM1KAzEQx4Motn4cfAHZi9KCq5lNk22OuvhRKChaP24hTaawuu3WZFfaN_DsI_okRrbUi6f5w_xmhvkRcgD0FGgCZ7mhQEFyt0HawBMac6Avm6RNacgghGyRHe9fKaWS9cQ2aQFwLqlgbfKUlaWz-UxX-QcWy-hx5nVVO12hjZ47g6fu9-fXRe4786XLA4bdKCun8wIX6E8iHd2jNr-T0UNZO4NROWmm9sjWRBce91d1lzxeXY6ym3h4ez3IzoexZj1ZxQhSS5YCgx6zkEiwog_MWgyJUy4nKBKZCCMSpvt9Nrbh3TR0TGqt0TRhu-S42Tt35XuNvlLT3BssCj3DsvYqBUglT3sB7DagcaX3Didq7vKpdksFVP1KVGuJgT1cLa3HU7R_5MpaAOIGyH2Fi3VfuzclUpZyNbp7UCMY3sA1fVFZ4I8aXhuvXoOpWXDyz-Ef-KOGRg</recordid><startdate>20010924</startdate><enddate>20010924</enddate><creator>Mills, R. 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M</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mills, R. C</au><au>Wang, S. Y. S</au><au>Abboud, K. A</au><au>Boncella, J. M</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Coordinatively Unsaturated W(IV)−Bis(pyridine) Complexes, a Reactive Source of W(IV)</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg. Chem</addtitle><date>2001-09-24</date><risdate>2001</risdate><volume>40</volume><issue>20</issue><spage>5077</spage><epage>5082</epage><pages>5077-5082</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><abstract>Addition of 2 equiv of a σ-donor ligand (L = pyridine, 4-picoline, or quinoline) to complexes of the type [W(NPh)(η4-arene)(o-(Me3SiN)2C6H4)] (arene = CH3CH2C6H5 (3), CH3CH2CH2C6H5 (4)) gave the W(IV)L2 compounds, [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)2] (5), [W(NPh)(o-(Me3SiN)2C6H4)(p−C6H7N)2] (6), and [W(NPh)(o-(Me3SiN)2C6H4)(C9H7N)2] (7). Synthesis of compounds 5 and 6 by Na° reduction of [W(NPh)(o-(Me3SiN)2C6H4)Cl2] in the presence of 3 equiv of L (L = 5, pyridine or 6, 4-picoline) is also presented. Compounds 5, 6, and 7 display hindered rotation of the donor ligands about the W−N bonds, resulting from a steric interaction with the Me3Si groups of the diamide ligand. The coordinative unsaturation of 5 and 6 has also been explored. Compounds 5 and 6 readily react with either CO and PMe3 to generated the six coordinate complexes [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)2(CO)] (8a), [W(NPh)(o-(Me3SiN)2C6H4)(C6H7N)2(CO)] (8b), [W(NPh)(o-(Me3SiN)2C6H4)(C5H5N)(PMe3)2] (10a), and [W(NPh)(o-(Me3SiN)2C6H4)(C6H7N)(PMe3)2] (10b), respectively.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>11559063</pmid><doi>10.1021/ic010195r</doi><tpages>6</tpages></addata></record>
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title Coordinatively Unsaturated W(IV)−Bis(pyridine) Complexes, a Reactive Source of W(IV)
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