Electronic and stereochemical factors contributing to the lability of trans-aquomethyl(tetraazamacrocycle) cobalt(III) complexes. Kinetic and molecular mechanics studies
The origin and variability of the trans-labilizing influence of the Co-alkyl bond have been investigated by using the anation reactions of a series of trans-Co(N{sub 4})(OH{sub 2})CH{sub 3}{sup 2+} (N{sub 4} is a tetraazamacrocyclic ligand) complexes as probes. Anation reactions of some related tran...
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| Veröffentlicht in: | Journal of the American Chemical Society 1989-09, Vol.111 (19), p.7411-7420 |
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| creator | Endicott, John F Kumar, Krishan Schwarz, Carolyn L Perkovic, Marc W Lin, Wang Kan |
| description | The origin and variability of the trans-labilizing influence of the Co-alkyl bond have been investigated by using the anation reactions of a series of trans-Co(N{sub 4})(OH{sub 2})CH{sub 3}{sup 2+} (N{sub 4} is a tetraazamacrocyclic ligand) complexes as probes. Anation reactions of some related trans-Co(N{sub 4})(OH{sub 2})Cl{sup 2+} complexes have also been examined to provide a basis for comparison with closely related, classical coordination complexes. A simple electrostatic model for substitution in Co(N{sub 4})(OH{sub 2}){sub 2}{sup 2+}, Co(N{sub 4})(OH{sub 2})CH{sub 3}{sup 2+}, and Co(N{sub 4})(OH{sub 2})Cl{sup 2+} complexes suggests that r{sub TS} may be only about 0.1 {angstrom} longer for substitution at the stereochemically cluttered site of Co(Me{sub 6}(14)dieneN{sub 4})(OH{sub 2})CH{sub 3}{sup 2+} than the uncluttered site. The methyl-aquo complexes are in the middle of this correlation, implying that the effective electron density at the cobalt center of these complexes is intermediate between that of the classical Co(III) and Co(II) coordination complexes. |
| doi_str_mv | 10.1021/ja00201a021 |
| format | Article |
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Kinetic and molecular mechanics studies</title><source>American Chemical Society (ACS) Journals</source><creator>Endicott, John F ; Kumar, Krishan ; Schwarz, Carolyn L ; Perkovic, Marc W ; Lin, Wang Kan</creator><creatorcontrib>Endicott, John F ; Kumar, Krishan ; Schwarz, Carolyn L ; Perkovic, Marc W ; Lin, Wang Kan</creatorcontrib><description>The origin and variability of the trans-labilizing influence of the Co-alkyl bond have been investigated by using the anation reactions of a series of trans-Co(N{sub 4})(OH{sub 2})CH{sub 3}{sup 2+} (N{sub 4} is a tetraazamacrocyclic ligand) complexes as probes. Anation reactions of some related trans-Co(N{sub 4})(OH{sub 2})Cl{sup 2+} complexes have also been examined to provide a basis for comparison with closely related, classical coordination complexes. A simple electrostatic model for substitution in Co(N{sub 4})(OH{sub 2}){sub 2}{sup 2+}, Co(N{sub 4})(OH{sub 2})CH{sub 3}{sup 2+}, and Co(N{sub 4})(OH{sub 2})Cl{sup 2+} complexes suggests that r{sub TS} may be only about 0.1 {angstrom} longer for substitution at the stereochemically cluttered site of Co(Me{sub 6}(14)dieneN{sub 4})(OH{sub 2})CH{sub 3}{sup 2+} than the uncluttered site. The methyl-aquo complexes are in the middle of this correlation, implying that the effective electron density at the cobalt center of these complexes is intermediate between that of the classical Co(III) and Co(II) coordination complexes.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja00201a021</identifier><identifier>CODEN: JACSAT</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>400200 -- Inorganic, Organic, & Physical Chemistry ; CALCULATION METHODS ; CHEMICAL REACTIONS ; Chemistry ; COBALT COMPLEXES ; COMPLEXES ; COORDINATION VALENCES ; DATA ; DATA ANALYSIS ; ELECTRONIC STRUCTURE ; Exact sciences and technology ; EXPERIMENTAL DATA ; INFORMATION ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; Kinetics and mechanisms ; LIGANDS ; MATERIALS SCIENCE ; MEASURING INSTRUMENTS ; MEASURING METHODS ; NUMERICAL DATA ; Organic chemistry ; Reactivity and mechanisms ; STEREOCHEMISTRY ; TRANSITION ELEMENT COMPLEXES ; VALENCE 360104 -- Metals & Alloys-- Physical Properties</subject><ispartof>Journal of the American Chemical Society, 1989-09, Vol.111 (19), p.7411-7420</ispartof><rights>1990 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a357t-b5f41a6ff7da1037dae005df585bc48cbdb349e92c64b717b2db6326592a93183</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja00201a021$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja00201a021$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,780,784,885,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=6600709$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/6713429$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Endicott, John F</creatorcontrib><creatorcontrib>Kumar, Krishan</creatorcontrib><creatorcontrib>Schwarz, Carolyn L</creatorcontrib><creatorcontrib>Perkovic, Marc W</creatorcontrib><creatorcontrib>Lin, Wang Kan</creatorcontrib><title>Electronic and stereochemical factors contributing to the lability of trans-aquomethyl(tetraazamacrocycle) cobalt(III) complexes. Kinetic and molecular mechanics studies</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>The origin and variability of the trans-labilizing influence of the Co-alkyl bond have been investigated by using the anation reactions of a series of trans-Co(N{sub 4})(OH{sub 2})CH{sub 3}{sup 2+} (N{sub 4} is a tetraazamacrocyclic ligand) complexes as probes. Anation reactions of some related trans-Co(N{sub 4})(OH{sub 2})Cl{sup 2+} complexes have also been examined to provide a basis for comparison with closely related, classical coordination complexes. A simple electrostatic model for substitution in Co(N{sub 4})(OH{sub 2}){sub 2}{sup 2+}, Co(N{sub 4})(OH{sub 2})CH{sub 3}{sup 2+}, and Co(N{sub 4})(OH{sub 2})Cl{sup 2+} complexes suggests that r{sub TS} may be only about 0.1 {angstrom} longer for substitution at the stereochemically cluttered site of Co(Me{sub 6}(14)dieneN{sub 4})(OH{sub 2})CH{sub 3}{sup 2+} than the uncluttered site. The methyl-aquo complexes are in the middle of this correlation, implying that the effective electron density at the cobalt center of these complexes is intermediate between that of the classical Co(III) and Co(II) coordination complexes.</description><subject>400200 -- Inorganic, Organic, & Physical Chemistry</subject><subject>CALCULATION METHODS</subject><subject>CHEMICAL REACTIONS</subject><subject>Chemistry</subject><subject>COBALT COMPLEXES</subject><subject>COMPLEXES</subject><subject>COORDINATION VALENCES</subject><subject>DATA</subject><subject>DATA ANALYSIS</subject><subject>ELECTRONIC STRUCTURE</subject><subject>Exact sciences and technology</subject><subject>EXPERIMENTAL DATA</subject><subject>INFORMATION</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>Kinetics and mechanisms</subject><subject>LIGANDS</subject><subject>MATERIALS SCIENCE</subject><subject>MEASURING INSTRUMENTS</subject><subject>MEASURING METHODS</subject><subject>NUMERICAL DATA</subject><subject>Organic chemistry</subject><subject>Reactivity and mechanisms</subject><subject>STEREOCHEMISTRY</subject><subject>TRANSITION ELEMENT COMPLEXES</subject><subject>VALENCE 360104 -- Metals & Alloys-- Physical Properties</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1989</creationdate><recordtype>article</recordtype><recordid>eNptkc9u1DAQxiMEEkvhxAtYCIlWKMV24vw5orbAspWo1HK2xo7NenHixXakLm_EWzKrVBUHLvbY_nnmm2-K4jWj54xy9mEHlHLKAOMnxYoJTkvBePO0WFF8KNuuqZ4XL1La4bHmHVsVf6680TmGyWkC00BSNtEEvTWj0-CJBZ1DTESHKUen5uymHyQHkreGeFDOu3wgwZIcYUol_JrDaPL24E-zwSv4DSPoGPRBe3OGSRT4fLper4_xuPfm3qRzsnGTyQ_lx4ByZg-RjEZvAVUllDQPzqSXxTMLPplXD_tJ8f3T1d3Fl_L62-f1xcfrEirR5lIJWzNorG0HYLTC1VAqBis6oXTdaTWoqu5Nz3VTq5a1ig-qqXgjeg59xbrqpHiz5A0pO5m0y6gE-5_QJ9m0rKp5j9D7BcLuUorGyn10I8SDZFQeRyH_GQXSbxd6DwldtWiWdunxS9NQ2tJj0nLBHE7h_vEZ4k-sW7VC3t3cysse468bITfIv1t40Enuwhwn9OW_Av4CHrun1Q</recordid><startdate>19890901</startdate><enddate>19890901</enddate><creator>Endicott, John F</creator><creator>Kumar, Krishan</creator><creator>Schwarz, Carolyn L</creator><creator>Perkovic, Marc W</creator><creator>Lin, Wang Kan</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>19890901</creationdate><title>Electronic and stereochemical factors contributing to the lability of trans-aquomethyl(tetraazamacrocycle) cobalt(III) complexes. Kinetic and molecular mechanics studies</title><author>Endicott, John F ; Kumar, Krishan ; Schwarz, Carolyn L ; Perkovic, Marc W ; Lin, Wang Kan</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a357t-b5f41a6ff7da1037dae005df585bc48cbdb349e92c64b717b2db6326592a93183</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1989</creationdate><topic>400200 -- Inorganic, Organic, & Physical Chemistry</topic><topic>CALCULATION METHODS</topic><topic>CHEMICAL REACTIONS</topic><topic>Chemistry</topic><topic>COBALT COMPLEXES</topic><topic>COMPLEXES</topic><topic>COORDINATION VALENCES</topic><topic>DATA</topic><topic>DATA ANALYSIS</topic><topic>ELECTRONIC STRUCTURE</topic><topic>Exact sciences and technology</topic><topic>EXPERIMENTAL DATA</topic><topic>INFORMATION</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>Kinetics and mechanisms</topic><topic>LIGANDS</topic><topic>MATERIALS SCIENCE</topic><topic>MEASURING INSTRUMENTS</topic><topic>MEASURING METHODS</topic><topic>NUMERICAL DATA</topic><topic>Organic chemistry</topic><topic>Reactivity and mechanisms</topic><topic>STEREOCHEMISTRY</topic><topic>TRANSITION ELEMENT COMPLEXES</topic><topic>VALENCE 360104 -- Metals & Alloys-- Physical Properties</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Endicott, John F</creatorcontrib><creatorcontrib>Kumar, Krishan</creatorcontrib><creatorcontrib>Schwarz, Carolyn L</creatorcontrib><creatorcontrib>Perkovic, Marc W</creatorcontrib><creatorcontrib>Lin, Wang Kan</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Endicott, John F</au><au>Kumar, Krishan</au><au>Schwarz, Carolyn L</au><au>Perkovic, Marc W</au><au>Lin, Wang Kan</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Electronic and stereochemical factors contributing to the lability of trans-aquomethyl(tetraazamacrocycle) cobalt(III) complexes. Kinetic and molecular mechanics studies</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>1989-09-01</date><risdate>1989</risdate><volume>111</volume><issue>19</issue><spage>7411</spage><epage>7420</epage><pages>7411-7420</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><coden>JACSAT</coden><abstract>The origin and variability of the trans-labilizing influence of the Co-alkyl bond have been investigated by using the anation reactions of a series of trans-Co(N{sub 4})(OH{sub 2})CH{sub 3}{sup 2+} (N{sub 4} is a tetraazamacrocyclic ligand) complexes as probes. Anation reactions of some related trans-Co(N{sub 4})(OH{sub 2})Cl{sup 2+} complexes have also been examined to provide a basis for comparison with closely related, classical coordination complexes. A simple electrostatic model for substitution in Co(N{sub 4})(OH{sub 2}){sub 2}{sup 2+}, Co(N{sub 4})(OH{sub 2})CH{sub 3}{sup 2+}, and Co(N{sub 4})(OH{sub 2})Cl{sup 2+} complexes suggests that r{sub TS} may be only about 0.1 {angstrom} longer for substitution at the stereochemically cluttered site of Co(Me{sub 6}(14)dieneN{sub 4})(OH{sub 2})CH{sub 3}{sup 2+} than the uncluttered site. The methyl-aquo complexes are in the middle of this correlation, implying that the effective electron density at the cobalt center of these complexes is intermediate between that of the classical Co(III) and Co(II) coordination complexes.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/ja00201a021</doi><tpages>10</tpages></addata></record> |
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| subjects | 400200 -- Inorganic, Organic, & Physical Chemistry CALCULATION METHODS CHEMICAL REACTIONS Chemistry COBALT COMPLEXES COMPLEXES COORDINATION VALENCES DATA DATA ANALYSIS ELECTRONIC STRUCTURE Exact sciences and technology EXPERIMENTAL DATA INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY Kinetics and mechanisms LIGANDS MATERIALS SCIENCE MEASURING INSTRUMENTS MEASURING METHODS NUMERICAL DATA Organic chemistry Reactivity and mechanisms STEREOCHEMISTRY TRANSITION ELEMENT COMPLEXES VALENCE 360104 -- Metals & Alloys-- Physical Properties |
| title | Electronic and stereochemical factors contributing to the lability of trans-aquomethyl(tetraazamacrocycle) cobalt(III) complexes. Kinetic and molecular mechanics studies |
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