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: 3098
Function: getPubMedXML
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
Severity: Warning
Message: Attempt to read property "Count" on bool
Filename: helpers/my_audit_helper.php
Line Number: 3100
Backtrace:
File: /var/www/html/application/helpers/my_audit_helper.php
Line: 3100
Function: _error_handler
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
While still rare, cationic ligands offer much promise as tunable electron-withdrawing ligands for π-acid catalysis. Recently, we introduced pincer-type sulfonium cations into the list of available strongly π-acidic ancillary ligands. However, the M-S bond in sulfonium complexes of these ligands was found highly labile, precluding their catalytic applications. Herein we demonstrate that this obstacle can be overcome by increasing the rigidity of the sulfonium pincer scaffold. X-ray analyses confirm that despite bearing a formal positive charge, the sulfur atom of this newly designed sulfonium ligand maintains its coordination to the Pt(II)-center, while DFT calculations indicate that by doing so it strongly enhances the electrophilic character of the metal. Kinetic studies carried out on three model cycloisomerization reactions prove that such a tris-cationic sulfonium-Pt(II) complex is highly reactive, compared to its thioether-based analogue. This proof-of-concept study presents the first example of employing sulfonium-based ligands in homogeneous catalysis.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1002/anie.202314997 | DOI Listing |
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!