{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,22]],"date-time":"2026-09-22T12:50:14Z","timestamp":1790081414623,"version":"4.0.1"},"reference-count":53,"publisher":"AIP Publishing","issue":"16","funder":[{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000288","name":"Royal Society","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100000288","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000774","name":"Newcastle University","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100000774","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000781","name":"European Research Council","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100000781","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2015,10,28]]},"abstract":"<jats:p>Strongly bound complexes (CH2)3\u22efMCl (M = Cu or Ag), formed by non-covalent interaction of cyclopropane and either cuprous chloride or argentous chloride, have been generated in the gas phase by means of the laser ablation of either copper or silver metal in the presence of supersonically expanded pulses of a gas mixture containing small amounts of cyclopropane and carbon tetrachloride in a large excess of argon. The rotational spectra of the complexes so formed were detected with a chirped-pulse, Fourier transform microwave spectrometer and analysed to give rotational constants and Cu and Cl nuclear quadrupole coupling constants for eight isotopologues of each of (CH2)3\u22efCuCl and (CH2)3\u22efAgCl. The geometry of each of these complexes was established unambiguously to have C2v symmetry, with the three C atoms coplanar, and with the MCl molecule lying along a median of the cyclopropane C3 triangle. This median coincides with the principal inertia axis a in each of the two complexes (CH2)3\u22efMCl. The M atom interacts with the pseudo-\u03c0 bond linking the pair of equivalent carbon atoms FC (F = front) nearest to it, so that M forms a non-covalent bond to one C\u2014C edge of the cyclopropane molecule. The (CH2)3\u22efMCl complexes have similar angular geometries to those of the hydrogen- and halogen-bonded analogues (CH2)3\u22efHCl and (CH2)3\u22efClF, respectively. Quantitative details of the geometries were determined by interpretation of the observed rotational constants and gave results in good agreement with those from ab initio calculations carried out at the CCSD(T)(F12*)\/aug-cc-pVTZ-F12 level of theory. Interesting geometrical features are the lengthening of the FC\u2014FC bond and the shrinkage of the two equivalent BC\u2014FC (B = back) bonds relative to the C\u2014C bond in cyclopropane itself. The expansions of the FC\u2014FC bond are 0.1024(9) \u00c5 and 0.0727(17) \u00c5 in (CH2)3\u22efCuCl and (CH2)3\u22efAgCl, respectively, according to the determined r0 geometries. The C\u2014C bond lengthening is in each case about four times that observed by similar methods in the corresponding complexes of MCl with ethyne and ethene, even though the cyclopropane complexes are more weakly bound than their ethyne and ethene analogues. Reasons for the larger increase in r(CC) in the pseudo-\u03c0 complexes are discussed.<\/jats:p>","DOI":"10.1063\/1.4934539","type":"journal-article","created":{"date-parts":[[2015,10,31]],"date-time":"2015-10-31T17:00:24Z","timestamp":1446310824000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":9,"title":["Interaction of a pseudo-\u03c0 C\u2014C bond with cuprous and argentous chlorides: Cyclopropane\u22efCuCl and cyclopropane\u22efAgCl investigated by rotational spectroscopy and <i>ab initio<\/i> calculations"],"prefix":"10.1063","volume":"143","author":[{"given":"Daniel P.","family":"Zaleski","sequence":"first","affiliation":[{"name":"Newcastle University 1 School of Chemistry, , Bedson Building, Newcastle-Upon-Tyne NE1 7RU, United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"John C.","family":"Mullaney","sequence":"additional","affiliation":[{"name":"Newcastle University 1 School of Chemistry, , Bedson Building, Newcastle-Upon-Tyne NE1 7RU, United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dror M.","family":"Bittner","sequence":"additional","affiliation":[{"name":"Newcastle University 1 School of Chemistry, , Bedson Building, Newcastle-Upon-Tyne NE1 7RU, United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"David P.","family":"Tew","sequence":"additional","affiliation":[{"name":"University of Bristol 2 School of Chemistry, , Bristol BS8 1TS, United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9450-305X","authenticated-orcid":false,"given":"Nicholas R.","family":"Walker","sequence":"additional","affiliation":[{"name":"Newcastle University 1 School of Chemistry, , Bedson Building, Newcastle-Upon-Tyne NE1 7RU, United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3468-9865","authenticated-orcid":false,"given":"Anthony C.","family":"Legon","sequence":"additional","affiliation":[{"name":"University of Bristol 2 School of Chemistry, , Bristol BS8 1TS, United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2015,10,30]]},"reference":[{"key":"2023061922274731600_c1","doi-asserted-by":"publisher","first-page":"1100","DOI":"10.1021\/ja043766y","volume":"127","year":"2005","journal-title":"J. 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