Kinetics of the reactions between [S(2)MoS(2)Cu(SC(6)H(4)R-4)](2-)(R = MeO, H, Cl or NO(2)) and CN(-): substitution mechanism at a 3-coordinate Cu(I) site
The kinetics of the reaction between [S(2)MoS(2)Cu(SC(6)H(4)R-4)](2-)(R = MeO, H, Cl or NO(2)) and CN(-) to form [S(2)MoS(2)CuCN](2-) have been studied in MeCN using stopped-flow spectrophotometry. In all cases, the rate law is of the form, Rate ={k+k(2)(R)[CN(-)]}[S(2)MoS(2)Cu(SC(6)H(4)R-4)(2-)]. I...
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Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2005-10 (19), p.3173-3178 |
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description | The kinetics of the reaction between [S(2)MoS(2)Cu(SC(6)H(4)R-4)](2-)(R = MeO, H, Cl or NO(2)) and CN(-) to form [S(2)MoS(2)CuCN](2-) have been studied in MeCN using stopped-flow spectrophotometry. In all cases, the rate law is of the form, Rate ={k+k(2)(R)[CN(-)]}[S(2)MoS(2)Cu(SC(6)H(4)R-4)(2-)]. It is proposed that both k and k correspond to associative substitution mechanisms. The k pathway involves attack by CN(-) at the copper site followed by dissociation of the thiolate. The k pathway involves attack of the solvent (MeCN) at the copper site, followed by dissociation of the thiolate to form [S(2)MoS(2)Cu(NCMe)](-). Subsequent rapid substitution of the coordinated solvent by cyanide produces [S(2)MoS(2)CuCN](2-). The evidence that both the k and k pathways involve associative mechanisms are: (i) the 4-R-substituent on the thiolate ligand has a similar effect on both k and k, with electron-withdrawing 4-R-substituents facilitating substitution; (ii) both the k and k pathways are associated with similar activation parameters (for k(1)(H): DeltaH++ = 5.5 +/- 0.5 kcal mol(-1), DeltaS++ = -23.9 +/- 2.0 cal deg(-1) mol(-1); for k(2)(H): DeltaH++ = 2.3 +/- 0.5 kcal mol(-1), DeltaS++ = - 23.9 +/- 2.0 cal deg(-1) mol(-1)) and (iii) addition of C(6)H(5)S(-) results in a similar increase in both k and k. |
doi_str_mv | 10.1039/b508389c |
format | Article |
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In all cases, the rate law is of the form, Rate ={k+k(2)(R)[CN(-)]}[S(2)MoS(2)Cu(SC(6)H(4)R-4)(2-)]. It is proposed that both k and k correspond to associative substitution mechanisms. The k pathway involves attack by CN(-) at the copper site followed by dissociation of the thiolate. The k pathway involves attack of the solvent (MeCN) at the copper site, followed by dissociation of the thiolate to form [S(2)MoS(2)Cu(NCMe)](-). Subsequent rapid substitution of the coordinated solvent by cyanide produces [S(2)MoS(2)CuCN](2-). The evidence that both the k and k pathways involve associative mechanisms are: (i) the 4-R-substituent on the thiolate ligand has a similar effect on both k and k, with electron-withdrawing 4-R-substituents facilitating substitution; (ii) both the k and k pathways are associated with similar activation parameters (for k(1)(H): DeltaH++ = 5.5 +/- 0.5 kcal mol(-1), DeltaS++ = -23.9 +/- 2.0 cal deg(-1) mol(-1); for k(2)(H): DeltaH++ = 2.3 +/- 0.5 kcal mol(-1), DeltaS++ = - 23.9 +/- 2.0 cal deg(-1) mol(-1)) and (iii) addition of C(6)H(5)S(-) results in a similar increase in both k and k.</description><identifier>ISSN: 1477-9226</identifier><identifier>DOI: 10.1039/b508389c</identifier><identifier>PMID: 16172642</identifier><language>eng</language><publisher>England</publisher><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2005-10 (19), p.3173-3178</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/16172642$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Lin, Ping</creatorcontrib><creatorcontrib>Smyth, Lynette</creatorcontrib><creatorcontrib>Waldram, Alison</creatorcontrib><creatorcontrib>Henderson, Richard A</creatorcontrib><title>Kinetics of the reactions between [S(2)MoS(2)Cu(SC(6)H(4)R-4)](2-)(R = MeO, H, Cl or NO(2)) and CN(-): substitution mechanism at a 3-coordinate Cu(I) site</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>The kinetics of the reaction between [S(2)MoS(2)Cu(SC(6)H(4)R-4)](2-)(R = MeO, H, Cl or NO(2)) and CN(-) to form [S(2)MoS(2)CuCN](2-) have been studied in MeCN using stopped-flow spectrophotometry. In all cases, the rate law is of the form, Rate ={k+k(2)(R)[CN(-)]}[S(2)MoS(2)Cu(SC(6)H(4)R-4)(2-)]. It is proposed that both k and k correspond to associative substitution mechanisms. The k pathway involves attack by CN(-) at the copper site followed by dissociation of the thiolate. The k pathway involves attack of the solvent (MeCN) at the copper site, followed by dissociation of the thiolate to form [S(2)MoS(2)Cu(NCMe)](-). Subsequent rapid substitution of the coordinated solvent by cyanide produces [S(2)MoS(2)CuCN](2-). The evidence that both the k and k pathways involve associative mechanisms are: (i) the 4-R-substituent on the thiolate ligand has a similar effect on both k and k, with electron-withdrawing 4-R-substituents facilitating substitution; (ii) both the k and k pathways are associated with similar activation parameters (for k(1)(H): DeltaH++ = 5.5 +/- 0.5 kcal mol(-1), DeltaS++ = -23.9 +/- 2.0 cal deg(-1) mol(-1); for k(2)(H): DeltaH++ = 2.3 +/- 0.5 kcal mol(-1), DeltaS++ = - 23.9 +/- 2.0 cal deg(-1) mol(-1)) and (iii) addition of C(6)H(5)S(-) results in a similar increase in both k and k.</description><issn>1477-9226</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><recordid>eNo1kN9KwzAchXOhuDkFn0B-V9LCqmmStqnghRR1w_2BTa9ESpKmLLK2s0kRX8WntcN5c87Nx3fgIHQR4usQ0_RGRphTnqojNAxZkgQpIfEAnVr7gTEhOCInaBDGYUJiRobo59nU2hlloSnBbTS0WihnmtqC1O5L6xre1h7x580-s85bZ17sTzzmrwLmv3sk8L0V3MFcL8cwGUO2haaFxbKHfRB1AdnCC_xbsJ20zrhur4ZKq42oja1AOBBAA9U0bWFq4TT0E1MfrHH6DB2XYmv1-aFH6PXx4SWbBLPl0zS7nwW7kDAXsCLFZchTSUVUxjGnCS4YL8uSUyE1LRMZKcx4RJIwjTCmmEeCF4TKQiomFaEjdPXn3bXNZ6etyytjld5uRa2bzuYxj_vjeNSDlwewk5Uu8l1rKtF-5_9v0l8EvWyZ</recordid><startdate>20051007</startdate><enddate>20051007</enddate><creator>Lin, Ping</creator><creator>Smyth, Lynette</creator><creator>Waldram, Alison</creator><creator>Henderson, Richard A</creator><scope>NPM</scope><scope>7X8</scope></search><sort><creationdate>20051007</creationdate><title>Kinetics of the reactions between [S(2)MoS(2)Cu(SC(6)H(4)R-4)](2-)(R = MeO, H, Cl or NO(2)) and CN(-): substitution mechanism at a 3-coordinate Cu(I) site</title><author>Lin, Ping ; Smyth, Lynette ; Waldram, Alison ; Henderson, Richard A</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-p124t-4d90f189b3a5f668370d48fff83abe3f7b5c048527195003085a8d23bdbc4bc23</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2005</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Lin, Ping</creatorcontrib><creatorcontrib>Smyth, Lynette</creatorcontrib><creatorcontrib>Waldram, Alison</creatorcontrib><creatorcontrib>Henderson, Richard A</creatorcontrib><collection>PubMed</collection><collection>MEDLINE - Academic</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Lin, Ping</au><au>Smyth, Lynette</au><au>Waldram, Alison</au><au>Henderson, Richard A</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Kinetics of the reactions between [S(2)MoS(2)Cu(SC(6)H(4)R-4)](2-)(R = MeO, H, Cl or NO(2)) and CN(-): substitution mechanism at a 3-coordinate Cu(I) site</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2005-10-07</date><risdate>2005</risdate><issue>19</issue><spage>3173</spage><epage>3178</epage><pages>3173-3178</pages><issn>1477-9226</issn><abstract>The kinetics of the reaction between [S(2)MoS(2)Cu(SC(6)H(4)R-4)](2-)(R = MeO, H, Cl or NO(2)) and CN(-) to form [S(2)MoS(2)CuCN](2-) have been studied in MeCN using stopped-flow spectrophotometry. In all cases, the rate law is of the form, Rate ={k+k(2)(R)[CN(-)]}[S(2)MoS(2)Cu(SC(6)H(4)R-4)(2-)]. It is proposed that both k and k correspond to associative substitution mechanisms. The k pathway involves attack by CN(-) at the copper site followed by dissociation of the thiolate. The k pathway involves attack of the solvent (MeCN) at the copper site, followed by dissociation of the thiolate to form [S(2)MoS(2)Cu(NCMe)](-). Subsequent rapid substitution of the coordinated solvent by cyanide produces [S(2)MoS(2)CuCN](2-). The evidence that both the k and k pathways involve associative mechanisms are: (i) the 4-R-substituent on the thiolate ligand has a similar effect on both k and k, with electron-withdrawing 4-R-substituents facilitating substitution; (ii) both the k and k pathways are associated with similar activation parameters (for k(1)(H): DeltaH++ = 5.5 +/- 0.5 kcal mol(-1), DeltaS++ = -23.9 +/- 2.0 cal deg(-1) mol(-1); for k(2)(H): DeltaH++ = 2.3 +/- 0.5 kcal mol(-1), DeltaS++ = - 23.9 +/- 2.0 cal deg(-1) mol(-1)) and (iii) addition of C(6)H(5)S(-) results in a similar increase in both k and k.</abstract><cop>England</cop><pmid>16172642</pmid><doi>10.1039/b508389c</doi><tpages>6</tpages></addata></record> |
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title | Kinetics of the reactions between [S(2)MoS(2)Cu(SC(6)H(4)R-4)](2-)(R = MeO, H, Cl or NO(2)) and CN(-): substitution mechanism at a 3-coordinate Cu(I) site |
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