The macrotricyclic title compound, C(36)H(64)N(4)O(14)·2C(6)H(6), is located on a crystallographic center of symmetry. The mol-ecule has four tertiary amide bridgehead atoms and consists of two unsymmetrical 20-membered diaza-tetra-oxamacrocycles (N(2)O(4) donor atom set) connected through the N atoms by two lateral oxydiethyl-ene bridges. The bridging subunits, together with the short bridging strand (NCCOCCN) from each monocycle, define a 24-membered ring (N(4)O(4) donor atom set) that forms a central cavity.
Kinetic addition of nucleophiles occurs at the center carbon of η3-propargyl rhenium complexes to produce rhenacyclobutenes. Reaction of P(CH3)3 with C5Me5(CO)2Re[η3-CH2C⋮CC(CH3)3]+BF4- (3a) gave the metallacyclobutene C5Me5(CO)2ReCH2C(PMe3)CC(CH3)3+BF4- (4a), which was characterized by X-ray crystallography. Malonate and acetylide nucleophiles reacted with C5Me5(CO)2Re[η3-CH2C⋮CCH3]+PF6- (3b) to give metallacyclobutene complexes. Pyridine added to the central propargyl carbon of 3b at low temperature to produce the metastable metallacyclobutene C5Me5(CO)2ReCH2C(NC5H5)CCH3+PF6- (14b) which rearranged to the η2-allene complex C5Me5(CO)2Re[η2-H2CCC(NC5H5)CH3]+PF6- (15K) at room temperature. 4-(Dimethylamino)pyridine (DMAP) added to the central carbon of the tert-butyl-substituted η3-propargyl complex 3a below −38 °C to give the rhenacyclobutene complex C5Me5(CO)2ReCH2C(NC5H4NMe2)CC(CH3)3+BF4- (22a) which rearranged to the η2-alkyne complex C5Me5(CO)2Re[η2-(CH3)3CC⋮CCH2NC5H4NMe2]+BF4- (23) at room temperature. Reaction of water with C5Me5(CO)2Re[η3-CH2C⋮CH]+BF4- (3c) gave the hydroxyallyl complex C5Me5(CO)2Re[η3-CH2C(OH)CH2]+BF4- (29) by a process proposed to involve nucleophilic addition of water to the central propargyl carbon of 3c followed by protonation of the metallacyclobutene intermediate.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDimerization of bridgehead olefins formed from tricyclic cyclopropylidenesPhilip Warner, Suae-Chen Chang, Douglas R. Powell, and Robert A. JacobsonCite this: J. Am. Chem. Soc. 1980, 102, 15, 5125–5127Publication Date (Print):July 1, 1980Publication History Published online1 May 2002Published inissue 1 July 1980https://pubs.acs.org/doi/10.1021/ja00535a065https://doi.org/10.1021/ja00535a065research-articleACS PublicationsRequest reuse permissionsArticle Views52Altmetric-Citations12LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
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