Ortho-, Meta-, and Para-Directing Influence of Transition-Metal Fragments in 12-Vertex c loso-Cyclopentadienylmetallaheteroboranes:  Additive Nature of Structural Increments

Cyclopentadienylmetal fragments in 12-vertex closo-cyclopentadienylmetallaheteroboranes have a clear preference with respect to the positions relative to heteroatoms in the thermodynamically most stable isomer. Cyclopentadienyl derivatives of group 9 and 10 metals direct a carbon atom to meta and pa...

Full description

Saved in:
Bibliographic Details
Published in:Organometallics 2006-01, Vol.25 (2), p.485-490
Main Authors: Kiani, Farooq Ahmad, Hofmann, Matthias
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
cited_by cdi_FETCH-LOGICAL-a104u-3cc865bcf1aed0ab9f4137625b8edae43aa54516db7b3c94a4eeb739db96b6053
cites cdi_FETCH-LOGICAL-a104u-3cc865bcf1aed0ab9f4137625b8edae43aa54516db7b3c94a4eeb739db96b6053
container_end_page 490
container_issue 2
container_start_page 485
container_title Organometallics
container_volume 25
creator Kiani, Farooq Ahmad
Hofmann, Matthias
description Cyclopentadienylmetal fragments in 12-vertex closo-cyclopentadienylmetallaheteroboranes have a clear preference with respect to the positions relative to heteroatoms in the thermodynamically most stable isomer. Cyclopentadienyl derivatives of group 9 and 10 metals direct a carbon atom to meta and para positions, respectively. CpM fragments of two group 8 metals, i.e., Ru and Os, have the tendency to direct carbon atoms to meta positions, while that of Fe directs carbon atoms to ortho positions. By using increments for two general structural features, i.e., HetHet‘o (two heteroatoms at ortho positions) and HetHet‘m (two heteroatoms at meta positions), the relative stabilities of numerous isomers can be easily predicted. A comparison with DFT-computed relative stabilities of 101 metallaheteroboranes incorporating up to 4 heteroatoms shows good agreement:  the average and standard deviations of the values derived from increments are 1.4 and 1.9 kcal mol-1, respectively.
doi_str_mv 10.1021/om050814u
format article
fullrecord <record><control><sourceid>acs_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1021_om050814u</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>e47888266</sourcerecordid><originalsourceid>FETCH-LOGICAL-a104u-3cc865bcf1aed0ab9f4137625b8edae43aa54516db7b3c94a4eeb739db96b6053</originalsourceid><addsrcrecordid>eNptUMtKAzEUDaJgfSz8g2xcCEaTyTw67qS-CtUKPrbDTXLHTpkmkmTE7tz6Nf6TX-JUxZWrw-WeF4eQPcGPBE_EsVvwjA9F2q2RgcgSznKeinUy4EmRs0JKuUm2QphzzvNCJgPyMfVx5tghvcYIPYA19BY8sLPGo46NfaJjW7cdWo3U1fTegw1NbJxlK0VLLzw8LdDGQBtLRcIe0Ud8pZq2Ljg2WurWPfdvMA3aZbtYaVqYYUTvlOvNMJx8vr3TU2N61xekNxA7_x11F32n-6MPGVvt8Ttlh2zU0Abc_cVt8nBxfj-6YpPp5Xh0OmEgeNoxqfUwz5SuBaDhoMo6FbLIk0wN0QCmEiBLM5EbVSipyxRSRFXI0qgyVznP5DY5-PHV3oXgsa6efbMAv6wEr1ZLV39L99z9Hy7oUM1d523f7B_eF_9-gjk</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Ortho-, Meta-, and Para-Directing Influence of Transition-Metal Fragments in 12-Vertex c loso-Cyclopentadienylmetallaheteroboranes:  Additive Nature of Structural Increments</title><source>American Chemical Society:Jisc Collections:American Chemical Society Read &amp; Publish Agreement 2022-2024 (Reading list)</source><creator>Kiani, Farooq Ahmad ; Hofmann, Matthias</creator><creatorcontrib>Kiani, Farooq Ahmad ; Hofmann, Matthias</creatorcontrib><description>Cyclopentadienylmetal fragments in 12-vertex closo-cyclopentadienylmetallaheteroboranes have a clear preference with respect to the positions relative to heteroatoms in the thermodynamically most stable isomer. Cyclopentadienyl derivatives of group 9 and 10 metals direct a carbon atom to meta and para positions, respectively. CpM fragments of two group 8 metals, i.e., Ru and Os, have the tendency to direct carbon atoms to meta positions, while that of Fe directs carbon atoms to ortho positions. By using increments for two general structural features, i.e., HetHet‘o (two heteroatoms at ortho positions) and HetHet‘m (two heteroatoms at meta positions), the relative stabilities of numerous isomers can be easily predicted. A comparison with DFT-computed relative stabilities of 101 metallaheteroboranes incorporating up to 4 heteroatoms shows good agreement:  the average and standard deviations of the values derived from increments are 1.4 and 1.9 kcal mol-1, respectively.</description><identifier>ISSN: 0276-7333</identifier><identifier>EISSN: 1520-6041</identifier><identifier>DOI: 10.1021/om050814u</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Organometallics, 2006-01, Vol.25 (2), p.485-490</ispartof><rights>Copyright © 2006 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a104u-3cc865bcf1aed0ab9f4137625b8edae43aa54516db7b3c94a4eeb739db96b6053</citedby><cites>FETCH-LOGICAL-a104u-3cc865bcf1aed0ab9f4137625b8edae43aa54516db7b3c94a4eeb739db96b6053</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27903,27904</link.rule.ids></links><search><creatorcontrib>Kiani, Farooq Ahmad</creatorcontrib><creatorcontrib>Hofmann, Matthias</creatorcontrib><title>Ortho-, Meta-, and Para-Directing Influence of Transition-Metal Fragments in 12-Vertex c loso-Cyclopentadienylmetallaheteroboranes:  Additive Nature of Structural Increments</title><title>Organometallics</title><addtitle>Organometallics</addtitle><description>Cyclopentadienylmetal fragments in 12-vertex closo-cyclopentadienylmetallaheteroboranes have a clear preference with respect to the positions relative to heteroatoms in the thermodynamically most stable isomer. Cyclopentadienyl derivatives of group 9 and 10 metals direct a carbon atom to meta and para positions, respectively. CpM fragments of two group 8 metals, i.e., Ru and Os, have the tendency to direct carbon atoms to meta positions, while that of Fe directs carbon atoms to ortho positions. By using increments for two general structural features, i.e., HetHet‘o (two heteroatoms at ortho positions) and HetHet‘m (two heteroatoms at meta positions), the relative stabilities of numerous isomers can be easily predicted. A comparison with DFT-computed relative stabilities of 101 metallaheteroboranes incorporating up to 4 heteroatoms shows good agreement:  the average and standard deviations of the values derived from increments are 1.4 and 1.9 kcal mol-1, respectively.</description><issn>0276-7333</issn><issn>1520-6041</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2006</creationdate><recordtype>article</recordtype><recordid>eNptUMtKAzEUDaJgfSz8g2xcCEaTyTw67qS-CtUKPrbDTXLHTpkmkmTE7tz6Nf6TX-JUxZWrw-WeF4eQPcGPBE_EsVvwjA9F2q2RgcgSznKeinUy4EmRs0JKuUm2QphzzvNCJgPyMfVx5tghvcYIPYA19BY8sLPGo46NfaJjW7cdWo3U1fTegw1NbJxlK0VLLzw8LdDGQBtLRcIe0Ud8pZq2Ljg2WurWPfdvMA3aZbtYaVqYYUTvlOvNMJx8vr3TU2N61xekNxA7_x11F32n-6MPGVvt8Ttlh2zU0Abc_cVt8nBxfj-6YpPp5Xh0OmEgeNoxqfUwz5SuBaDhoMo6FbLIk0wN0QCmEiBLM5EbVSipyxRSRFXI0qgyVznP5DY5-PHV3oXgsa6efbMAv6wEr1ZLV39L99z9Hy7oUM1d523f7B_eF_9-gjk</recordid><startdate>20060116</startdate><enddate>20060116</enddate><creator>Kiani, Farooq Ahmad</creator><creator>Hofmann, Matthias</creator><general>American Chemical Society</general><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20060116</creationdate><title>Ortho-, Meta-, and Para-Directing Influence of Transition-Metal Fragments in 12-Vertex c loso-Cyclopentadienylmetallaheteroboranes:  Additive Nature of Structural Increments</title><author>Kiani, Farooq Ahmad ; Hofmann, Matthias</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a104u-3cc865bcf1aed0ab9f4137625b8edae43aa54516db7b3c94a4eeb739db96b6053</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2006</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kiani, Farooq Ahmad</creatorcontrib><creatorcontrib>Hofmann, Matthias</creatorcontrib><collection>CrossRef</collection><jtitle>Organometallics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kiani, Farooq Ahmad</au><au>Hofmann, Matthias</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Ortho-, Meta-, and Para-Directing Influence of Transition-Metal Fragments in 12-Vertex c loso-Cyclopentadienylmetallaheteroboranes:  Additive Nature of Structural Increments</atitle><jtitle>Organometallics</jtitle><addtitle>Organometallics</addtitle><date>2006-01-16</date><risdate>2006</risdate><volume>25</volume><issue>2</issue><spage>485</spage><epage>490</epage><pages>485-490</pages><issn>0276-7333</issn><eissn>1520-6041</eissn><abstract>Cyclopentadienylmetal fragments in 12-vertex closo-cyclopentadienylmetallaheteroboranes have a clear preference with respect to the positions relative to heteroatoms in the thermodynamically most stable isomer. Cyclopentadienyl derivatives of group 9 and 10 metals direct a carbon atom to meta and para positions, respectively. CpM fragments of two group 8 metals, i.e., Ru and Os, have the tendency to direct carbon atoms to meta positions, while that of Fe directs carbon atoms to ortho positions. By using increments for two general structural features, i.e., HetHet‘o (two heteroatoms at ortho positions) and HetHet‘m (two heteroatoms at meta positions), the relative stabilities of numerous isomers can be easily predicted. A comparison with DFT-computed relative stabilities of 101 metallaheteroboranes incorporating up to 4 heteroatoms shows good agreement:  the average and standard deviations of the values derived from increments are 1.4 and 1.9 kcal mol-1, respectively.</abstract><pub>American Chemical Society</pub><doi>10.1021/om050814u</doi><tpages>6</tpages></addata></record>
fulltext fulltext
identifier ISSN: 0276-7333
ispartof Organometallics, 2006-01, Vol.25 (2), p.485-490
issn 0276-7333
1520-6041
language eng
recordid cdi_crossref_primary_10_1021_om050814u
source American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)
title Ortho-, Meta-, and Para-Directing Influence of Transition-Metal Fragments in 12-Vertex c loso-Cyclopentadienylmetallaheteroboranes:  Additive Nature of Structural Increments
url http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-27T10%3A22%3A10IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-acs_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Ortho-,%20Meta-,%20and%20Para-Directing%20Influence%20of%20Transition-Metal%20Fragments%20in%2012-Vertex%20c%20loso-Cyclopentadienylmetallaheteroboranes:%E2%80%89%20Additive%20Nature%20of%20Structural%20Increments&rft.jtitle=Organometallics&rft.au=Kiani,%20Farooq%20Ahmad&rft.date=2006-01-16&rft.volume=25&rft.issue=2&rft.spage=485&rft.epage=490&rft.pages=485-490&rft.issn=0276-7333&rft.eissn=1520-6041&rft_id=info:doi/10.1021/om050814u&rft_dat=%3Cacs_cross%3Ee47888266%3C/acs_cross%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-a104u-3cc865bcf1aed0ab9f4137625b8edae43aa54516db7b3c94a4eeb739db96b6053%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true