Severity: Warning
Message: file_get_contents(https://...@gmail.com&api_key=61f08fa0b96a73de8c900d749fcb997acc09): Failed to open stream: HTTP request failed! HTTP/1.1 429 Too Many Requests
Filename: helpers/my_audit_helper.php
Line Number: 143
Backtrace:
File: /var/www/html/application/helpers/my_audit_helper.php
Line: 143
Function: file_get_contents
File: /var/www/html/application/helpers/my_audit_helper.php
Line: 209
Function: simplexml_load_file_from_url
File: /var/www/html/application/helpers/my_audit_helper.php
Line: 994
Function: getPubMedXML
File: /var/www/html/application/helpers/my_audit_helper.php
Line: 3134
Function: GetPubMedArticleOutput_2016
File: /var/www/html/application/controllers/Detail.php
Line: 574
Function: pubMedSearch_Global
File: /var/www/html/application/controllers/Detail.php
Line: 488
Function: pubMedGetRelatedKeyword
File: /var/www/html/index.php
Line: 316
Function: require_once
A bidentate nitrogen-donor ligand with an appended phenol group, CHNCH[double bond, length as m-dash]N-2-CHOH, H(L1) was treated with a palladium cycloneophyl complex [Pd(CHCMeCH)(COD)], with both Pd-aryl and Pd-alkyl bonds, to give a Pd-alkyl complex, [Pd(CHCMeCH)(κ-N,N',O-OCHN[double bond, length as m-dash]CH(2-CHN))], 1. The cleavage of the Pd-aryl bond and the deprotonation of the ligand phenol to afford a bound aryloxide, indicates facile Pd-aryl bond protonolysis. Deuterium labelling experiments confirmed that the ligand phenol promotes protonolysis and that the reverse, aryl C-H activation, occurs under very mild reaction conditions (within 10 min at room temperature). An unusual isomerization of the Pd-alkyl complex 1 to a Pd-aryl complex, [Pd(CH(2-t-Bu))(κ-N,N',O-OCHN[double bond, length as m-dash]CH(2-CHN))], 2, was observed to give an equilibrium with [2]/[1] = 9 after 5 days in methanol. The isomerization requires that both aryl C-H activation and Pd-alkyl protonolysis steps occur. The very large KIE value (k/k = ca. 40) for isomerization of 1 to 2, suggests a concerted S2-type mechanism for the Pd-alkyl protonolysis step.
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Source |
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http://dx.doi.org/10.1039/c8dt00437d | DOI Listing |
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