Homolysis and acidolysis reactions of (.alpha.-hydroxyalkyl)- and (.alpha.-alkoxyalkyl)chromium(III) complexes: kinetics, steric effects, and bond energies
The rates of homolysis of 12 organochromium complexes were determined by the addition of oxidizing scavengers to prevent recombination of Cr/sup 2 +/ and the carbon-centered radicals. The rate constants for complexes derived from aliphatic alcohols span the range 3.7 x 10/sup -5/to approx. 3 x 10/su...
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| Veröffentlicht in: | J. Am. Chem. Soc.; (United States) 1982-03, Vol.104 (5), p.1249-1255 |
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| creator | Kirker, Garry W Bakac, Andreja Espenson, James H |
| description | The rates of homolysis of 12 organochromium complexes were determined by the addition of oxidizing scavengers to prevent recombination of Cr/sup 2 +/ and the carbon-centered radicals. The rate constants for complexes derived from aliphatic alcohols span the range 3.7 x 10/sup -5/to approx. 3 x 10/sup 2/s/sup -1/ CrCH/sub 2/OH/sup 2 +/s/sup -1/ for CrC(CH/sub 3/)(t-C/sub 4/H/sub 9/)OH/sup 2 +/ at 25/sup 0/C. There is a good correlation between the free energies of activation for homolysis of the organochromium complexes and corresponding substituted symmetrical ethanes. On the basis of the activation parameters and the literature data, estimates of the Cr-C bond dissociation enthalpies were made. Rate constants for the acidolysis reaction, previously known for some of these complexes, were evaluated for the others. Means were developed, by control of reaction conditions, to permit independent measurements of homolysis and acidolysis. The organochromium complex derived from isopropyl ether, CrC(CH/sub 3/)/sub 2/OCH(CH/sub 3/)/sub 2//sup 2 +/, undergoes a rapid (0.05 < k < 2 s/sup -1/) conversion to CrC(CH/sub 3/)/sub 2/OH/sup 2 +/ in dilute perchloric acid. 5 figures, 6 tables. |
| doi_str_mv | 10.1021/ja00369a018 |
| format | Article |
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The rate constants for complexes derived from aliphatic alcohols span the range 3.7 x 10/sup -5/to approx. 3 x 10/sup 2/s/sup -1/ CrCH/sub 2/OH/sup 2 +/s/sup -1/ for CrC(CH/sub 3/)(t-C/sub 4/H/sub 9/)OH/sup 2 +/ at 25/sup 0/C. There is a good correlation between the free energies of activation for homolysis of the organochromium complexes and corresponding substituted symmetrical ethanes. On the basis of the activation parameters and the literature data, estimates of the Cr-C bond dissociation enthalpies were made. Rate constants for the acidolysis reaction, previously known for some of these complexes, were evaluated for the others. Means were developed, by control of reaction conditions, to permit independent measurements of homolysis and acidolysis. The organochromium complex derived from isopropyl ether, CrC(CH/sub 3/)/sub 2/OCH(CH/sub 3/)/sub 2//sup 2 +/, undergoes a rapid (0.05 < k < 2 s/sup -1/) conversion to CrC(CH/sub 3/)/sub 2/OH/sup 2 +/ in dilute perchloric acid. 5 figures, 6 tables.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja00369a018</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987) ; ACIDIFICATION ; ALCOHOLS ; ALKOXY RADICALS ; BINDING ENERGY ; CHEMICAL REACTION KINETICS ; CHROMIUM COMPLEXES ; COMPLEXES ; ENERGY ; HYDROXY COMPOUNDS ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; KINETICS ; ORGANIC COMPOUNDS ; ORGANOMETALLIC COMPOUNDS ; RADICALS ; REACTION KINETICS ; TRANSITION ELEMENT COMPLEXES</subject><ispartof>J. Am. Chem. Soc.; (United States), 1982-03, Vol.104 (5), p.1249-1255</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a311t-ec14605c6f6a972126d27c15173ee8cf9ce2630535027a1b33252a6efca2d0793</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/ja00369a018$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja00369a018$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,885,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/5611455$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Kirker, Garry W</creatorcontrib><creatorcontrib>Bakac, Andreja</creatorcontrib><creatorcontrib>Espenson, James H</creatorcontrib><creatorcontrib>Iowa State Univ., Ames</creatorcontrib><title>Homolysis and acidolysis reactions of (.alpha.-hydroxyalkyl)- and (.alpha.-alkoxyalkyl)chromium(III) complexes: kinetics, steric effects, and bond energies</title><title>J. Am. Chem. Soc.; (United States)</title><addtitle>J. Am. Chem. Soc</addtitle><description>The rates of homolysis of 12 organochromium complexes were determined by the addition of oxidizing scavengers to prevent recombination of Cr/sup 2 +/ and the carbon-centered radicals. The rate constants for complexes derived from aliphatic alcohols span the range 3.7 x 10/sup -5/to approx. 3 x 10/sup 2/s/sup -1/ CrCH/sub 2/OH/sup 2 +/s/sup -1/ for CrC(CH/sub 3/)(t-C/sub 4/H/sub 9/)OH/sup 2 +/ at 25/sup 0/C. There is a good correlation between the free energies of activation for homolysis of the organochromium complexes and corresponding substituted symmetrical ethanes. On the basis of the activation parameters and the literature data, estimates of the Cr-C bond dissociation enthalpies were made. Rate constants for the acidolysis reaction, previously known for some of these complexes, were evaluated for the others. Means were developed, by control of reaction conditions, to permit independent measurements of homolysis and acidolysis. The organochromium complex derived from isopropyl ether, CrC(CH/sub 3/)/sub 2/OCH(CH/sub 3/)/sub 2//sup 2 +/, undergoes a rapid (0.05 < k < 2 s/sup -1/) conversion to CrC(CH/sub 3/)/sub 2/OH/sup 2 +/ in dilute perchloric acid. 5 figures, 6 tables.</description><subject>400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)</subject><subject>ACIDIFICATION</subject><subject>ALCOHOLS</subject><subject>ALKOXY RADICALS</subject><subject>BINDING ENERGY</subject><subject>CHEMICAL REACTION KINETICS</subject><subject>CHROMIUM COMPLEXES</subject><subject>COMPLEXES</subject><subject>ENERGY</subject><subject>HYDROXY COMPOUNDS</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>KINETICS</subject><subject>ORGANIC COMPOUNDS</subject><subject>ORGANOMETALLIC COMPOUNDS</subject><subject>RADICALS</subject><subject>REACTION KINETICS</subject><subject>TRANSITION ELEMENT COMPLEXES</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1982</creationdate><recordtype>article</recordtype><recordid>eNptkM9OGzEQxi1EpQbaU19gxaUg2NR_Ym_SWwWkiYjUIsLZGmZniZPddWQvUvZZ-rKYBkU99DLW5_nNp_mGsS-CDwWX4tsaOFdmAlyMj9hAaMlzLaQ5ZgPOucyLsVEf2UmM6yRHciwG7M_MN77uo4sZtGUG6Mp3GQiwc76Nma-y8yHU2xUM81VfBr_rod709UX-d-bQS5-HFq6Cb9xLcz6fzy8y9M22ph3F79nGtdQ5jFdZ7Cg4zKiqCLuk37yefCrUUnh2FD-xDxXUkT6_v6fscXq7vJ7li18_59c_FjkoIbqcUIwM12gqA5NCprylLFBoUSiiMVYTJGkU10pzWYB4UkpqCYYqBFnyYqJO2dne18fO2YiuI1yhb9u0l9VGiJHWCbrcQxh8jIEquw2ugdBbwe3b8e0_x090vqddSrk7oBA21hSq0Hb5-8EqebPQd8upvU_81z0PGO3av4Q2Bf6v8yvYWpN0</recordid><startdate>198203</startdate><enddate>198203</enddate><creator>Kirker, Garry W</creator><creator>Bakac, Andreja</creator><creator>Espenson, James H</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>198203</creationdate><title>Homolysis and acidolysis reactions of (.alpha.-hydroxyalkyl)- and (.alpha.-alkoxyalkyl)chromium(III) complexes: kinetics, steric effects, and bond energies</title><author>Kirker, Garry W ; Bakac, Andreja ; Espenson, James H</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a311t-ec14605c6f6a972126d27c15173ee8cf9ce2630535027a1b33252a6efca2d0793</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1982</creationdate><topic>400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)</topic><topic>ACIDIFICATION</topic><topic>ALCOHOLS</topic><topic>ALKOXY RADICALS</topic><topic>BINDING ENERGY</topic><topic>CHEMICAL REACTION KINETICS</topic><topic>CHROMIUM COMPLEXES</topic><topic>COMPLEXES</topic><topic>ENERGY</topic><topic>HYDROXY COMPOUNDS</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>KINETICS</topic><topic>ORGANIC COMPOUNDS</topic><topic>ORGANOMETALLIC COMPOUNDS</topic><topic>RADICALS</topic><topic>REACTION KINETICS</topic><topic>TRANSITION ELEMENT COMPLEXES</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kirker, Garry W</creatorcontrib><creatorcontrib>Bakac, Andreja</creatorcontrib><creatorcontrib>Espenson, James H</creatorcontrib><creatorcontrib>Iowa State Univ., Ames</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>J. Am. Chem. Soc.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kirker, Garry W</au><au>Bakac, Andreja</au><au>Espenson, James H</au><aucorp>Iowa State Univ., Ames</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Homolysis and acidolysis reactions of (.alpha.-hydroxyalkyl)- and (.alpha.-alkoxyalkyl)chromium(III) complexes: kinetics, steric effects, and bond energies</atitle><jtitle>J. Am. Chem. Soc.; (United States)</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>1982-03</date><risdate>1982</risdate><volume>104</volume><issue>5</issue><spage>1249</spage><epage>1255</epage><pages>1249-1255</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>The rates of homolysis of 12 organochromium complexes were determined by the addition of oxidizing scavengers to prevent recombination of Cr/sup 2 +/ and the carbon-centered radicals. The rate constants for complexes derived from aliphatic alcohols span the range 3.7 x 10/sup -5/to approx. 3 x 10/sup 2/s/sup -1/ CrCH/sub 2/OH/sup 2 +/s/sup -1/ for CrC(CH/sub 3/)(t-C/sub 4/H/sub 9/)OH/sup 2 +/ at 25/sup 0/C. There is a good correlation between the free energies of activation for homolysis of the organochromium complexes and corresponding substituted symmetrical ethanes. On the basis of the activation parameters and the literature data, estimates of the Cr-C bond dissociation enthalpies were made. Rate constants for the acidolysis reaction, previously known for some of these complexes, were evaluated for the others. Means were developed, by control of reaction conditions, to permit independent measurements of homolysis and acidolysis. The organochromium complex derived from isopropyl ether, CrC(CH/sub 3/)/sub 2/OCH(CH/sub 3/)/sub 2//sup 2 +/, undergoes a rapid (0.05 < k < 2 s/sup -1/) conversion to CrC(CH/sub 3/)/sub 2/OH/sup 2 +/ in dilute perchloric acid. 5 figures, 6 tables.</abstract><cop>United States</cop><pub>American Chemical Society</pub><doi>10.1021/ja00369a018</doi><tpages>7</tpages></addata></record> |
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| source | ACS Publications |
| subjects | 400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987) ACIDIFICATION ALCOHOLS ALKOXY RADICALS BINDING ENERGY CHEMICAL REACTION KINETICS CHROMIUM COMPLEXES COMPLEXES ENERGY HYDROXY COMPOUNDS INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY KINETICS ORGANIC COMPOUNDS ORGANOMETALLIC COMPOUNDS RADICALS REACTION KINETICS TRANSITION ELEMENT COMPLEXES |
| title | Homolysis and acidolysis reactions of (.alpha.-hydroxyalkyl)- and (.alpha.-alkoxyalkyl)chromium(III) complexes: kinetics, steric effects, and bond energies |
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