Preferred orientation of imidazole ligands in metalloporphyrins
Recent work has suggested that axial ligand orientation can affect the physiocochemical properties of metalloporphyrins. Analysis of crystallographic data indicates that axial imidazole ligands in metalloporphyrins tend to prefer sterically unfavorable orientations that eclipse equatorial M-N/sub p/...
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| Veröffentlicht in: | J. Am. Chem. Soc.; (United States) 1986-03, Vol.108 (6), p.1163-1167 |
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| container_title | J. Am. Chem. Soc.; (United States) |
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| creator | Scheidt, W. Robert Chipman, Daniel M |
| description | Recent work has suggested that axial ligand orientation can affect the physiocochemical properties of metalloporphyrins. Analysis of crystallographic data indicates that axial imidazole ligands in metalloporphyrins tend to prefer sterically unfavorable orientations that eclipse equatorial M-N/sub p/ bonds. Charge iterative extended Hueckel theory calculations on electronic effects for a broad selection of representative systems indicate a previously unrecognized orientational preference in the M-N(imidazole) ..pi.. bond which favors eclipsed orientations. Somewhat surprisingly, this ..pi.. bond is found to be dominated by the metal p..pi..-imidazole p..pi.. interaction. These theoretical results provide an explanation of the mystery of why the orientation effect seems to be insensitive to metal d/sup n/ configuration, spin state, oxidation state, and the presence or absence of a sixth axial ligand. 23 references, 1 figure, 3 tables. |
| doi_str_mv | 10.1021/ja00266a008 |
| format | Article |
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These theoretical results provide an explanation of the mystery of why the orientation effect seems to be insensitive to metal d/sup n/ configuration, spin state, oxidation state, and the presence or absence of a sixth axial ligand. 23 references, 1 figure, 3 tables.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja00266a008</identifier><identifier>CODEN: JACSAT</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987) ; Atomic and molecular physics ; AZOLES ; Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) ; CARBOXYLIC ACIDS ; CONFIGURATION INTERACTION ; DATA ; ELECTRONIC STRUCTURE ; Electronic structure of atoms, molecules and their ions: theory ; ENERGY LEVELS ; Exact sciences and technology ; HETEROCYCLIC ACIDS ; HETEROCYCLIC COMPOUNDS ; IMIDAZOLES ; INFORMATION ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; LIGANDS ; NUMERICAL DATA ; ORGANIC ACIDS ; ORGANIC COMPOUNDS ; ORGANIC NITROGEN COMPOUNDS ; ORGANOMETALLIC COMPOUNDS ; Physics ; PORPHYRINS ; Semi-empirical and empirical calculations (differential overlap, hückel, ppp methods, etc.) ; THEORETICAL DATA ; VALENCE</subject><ispartof>J. 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Robert</creatorcontrib><creatorcontrib>Chipman, Daniel M</creatorcontrib><creatorcontrib>Univ. of Notre Dame, IN</creatorcontrib><title>Preferred orientation of imidazole ligands in metalloporphyrins</title><title>J. Am. Chem. Soc.; (United States)</title><addtitle>J. Am. Chem. Soc</addtitle><description>Recent work has suggested that axial ligand orientation can affect the physiocochemical properties of metalloporphyrins. Analysis of crystallographic data indicates that axial imidazole ligands in metalloporphyrins tend to prefer sterically unfavorable orientations that eclipse equatorial M-N/sub p/ bonds. Charge iterative extended Hueckel theory calculations on electronic effects for a broad selection of representative systems indicate a previously unrecognized orientational preference in the M-N(imidazole) ..pi.. bond which favors eclipsed orientations. Somewhat surprisingly, this ..pi.. bond is found to be dominated by the metal p..pi..-imidazole p..pi.. interaction. These theoretical results provide an explanation of the mystery of why the orientation effect seems to be insensitive to metal d/sup n/ configuration, spin state, oxidation state, and the presence or absence of a sixth axial ligand. 23 references, 1 figure, 3 tables.</description><subject>400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)</subject><subject>Atomic and molecular physics</subject><subject>AZOLES</subject><subject>Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations)</subject><subject>CARBOXYLIC ACIDS</subject><subject>CONFIGURATION INTERACTION</subject><subject>DATA</subject><subject>ELECTRONIC STRUCTURE</subject><subject>Electronic structure of atoms, molecules and their ions: theory</subject><subject>ENERGY LEVELS</subject><subject>Exact sciences and technology</subject><subject>HETEROCYCLIC ACIDS</subject><subject>HETEROCYCLIC COMPOUNDS</subject><subject>IMIDAZOLES</subject><subject>INFORMATION</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>LIGANDS</subject><subject>NUMERICAL DATA</subject><subject>ORGANIC ACIDS</subject><subject>ORGANIC COMPOUNDS</subject><subject>ORGANIC NITROGEN COMPOUNDS</subject><subject>ORGANOMETALLIC COMPOUNDS</subject><subject>Physics</subject><subject>PORPHYRINS</subject><subject>Semi-empirical and empirical calculations (differential overlap, hückel, ppp methods, etc.)</subject><subject>THEORETICAL DATA</subject><subject>VALENCE</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1986</creationdate><recordtype>article</recordtype><recordid>eNptkE9LAzEQxYMoWKsnv8AiggdZTTZ_9yRStQoFiy0UvIQ0m7Wp22RJVrB-eiMrxYOXGYb3m2HeA-AUwSsEC3S9VhAWjKUq9sAA0QLmFBVsHwxgEnIuGD4ERzGu00gKgQbgZhpMbUIwVeaDNa5TnfUu83VmN7ZSX74xWWPflKtiZl22MZ1qGt_60K62wbp4DA5q1URz8tuHYPZwPx895pPn8dPodpIrUuAuF5pUJcaVQRrRmlSYsooZU3BUIEx4rRgWJedLusSKVyhZoFoIs2S0FqLGQ3DWX_WxszJq2xm90t45oztJSclhWSbosod08DEmW7INdqPCViIof-KRf-JJ9HlPtypq1dRBOW3jboWXBFKCEpb3mI2d-dzJKrxLxjGncj6dycWI3Ynx4lW-JP6i55WOcu0_gkup_PvAN_tbf_o</recordid><startdate>198603</startdate><enddate>198603</enddate><creator>Scheidt, W. Robert</creator><creator>Chipman, Daniel M</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>198603</creationdate><title>Preferred orientation of imidazole ligands in metalloporphyrins</title><author>Scheidt, W. Robert ; Chipman, Daniel M</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a423t-8c4d933de1c15f4d356d6ee27121347fa638977b5b3a7d166a5c88eb65f88f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1986</creationdate><topic>400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)</topic><topic>Atomic and molecular physics</topic><topic>AZOLES</topic><topic>Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations)</topic><topic>CARBOXYLIC ACIDS</topic><topic>CONFIGURATION INTERACTION</topic><topic>DATA</topic><topic>ELECTRONIC STRUCTURE</topic><topic>Electronic structure of atoms, molecules and their ions: theory</topic><topic>ENERGY LEVELS</topic><topic>Exact sciences and technology</topic><topic>HETEROCYCLIC ACIDS</topic><topic>HETEROCYCLIC COMPOUNDS</topic><topic>IMIDAZOLES</topic><topic>INFORMATION</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>LIGANDS</topic><topic>NUMERICAL DATA</topic><topic>ORGANIC ACIDS</topic><topic>ORGANIC COMPOUNDS</topic><topic>ORGANIC NITROGEN COMPOUNDS</topic><topic>ORGANOMETALLIC COMPOUNDS</topic><topic>Physics</topic><topic>PORPHYRINS</topic><topic>Semi-empirical and empirical calculations (differential overlap, hückel, ppp methods, etc.)</topic><topic>THEORETICAL DATA</topic><topic>VALENCE</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Scheidt, W. Robert</creatorcontrib><creatorcontrib>Chipman, Daniel M</creatorcontrib><creatorcontrib>Univ. of Notre Dame, IN</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</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>Scheidt, W. Robert</au><au>Chipman, Daniel M</au><aucorp>Univ. of Notre Dame, IN</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Preferred orientation of imidazole ligands in metalloporphyrins</atitle><jtitle>J. Am. Chem. Soc.; (United States)</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>1986-03</date><risdate>1986</risdate><volume>108</volume><issue>6</issue><spage>1163</spage><epage>1167</epage><pages>1163-1167</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><coden>JACSAT</coden><abstract>Recent work has suggested that axial ligand orientation can affect the physiocochemical properties of metalloporphyrins. Analysis of crystallographic data indicates that axial imidazole ligands in metalloporphyrins tend to prefer sterically unfavorable orientations that eclipse equatorial M-N/sub p/ bonds. Charge iterative extended Hueckel theory calculations on electronic effects for a broad selection of representative systems indicate a previously unrecognized orientational preference in the M-N(imidazole) ..pi.. bond which favors eclipsed orientations. Somewhat surprisingly, this ..pi.. bond is found to be dominated by the metal p..pi..-imidazole p..pi.. interaction. These theoretical results provide an explanation of the mystery of why the orientation effect seems to be insensitive to metal d/sup n/ configuration, spin state, oxidation state, and the presence or absence of a sixth axial ligand. 23 references, 1 figure, 3 tables.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/ja00266a008</doi><tpages>5</tpages></addata></record> |
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| identifier | ISSN: 0002-7863 |
| ispartof | J. Am. Chem. Soc.; (United States), 1986-03, Vol.108 (6), p.1163-1167 |
| issn | 0002-7863 1520-5126 |
| language | eng |
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| source | American Chemical Society Journals |
| subjects | 400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987) Atomic and molecular physics AZOLES Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) CARBOXYLIC ACIDS CONFIGURATION INTERACTION DATA ELECTRONIC STRUCTURE Electronic structure of atoms, molecules and their ions: theory ENERGY LEVELS Exact sciences and technology HETEROCYCLIC ACIDS HETEROCYCLIC COMPOUNDS IMIDAZOLES INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY LIGANDS NUMERICAL DATA ORGANIC ACIDS ORGANIC COMPOUNDS ORGANIC NITROGEN COMPOUNDS ORGANOMETALLIC COMPOUNDS Physics PORPHYRINS Semi-empirical and empirical calculations (differential overlap, hückel, ppp methods, etc.) THEORETICAL DATA VALENCE |
| title | Preferred orientation of imidazole ligands in metalloporphyrins |
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