{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,10]],"date-time":"2026-06-10T15:48:59Z","timestamp":1781106539363,"version":"3.54.1"},"reference-count":45,"publisher":"National Academy of Sciences","issue":"17","content-domain":{"domain":["www.pnas.org"],"crossmark-restriction":true},"short-container-title":["Proc. Natl. Acad. Sci. U.S.A."],"published-print":{"date-parts":[[2007,4,24]]},"abstract":"<jats:p>\n                    The complex [Rh(O\n                    <jats:sub>2<\/jats:sub>\n                    Cisoq)(H)(SnPh\n                    <jats:sub>3<\/jats:sub>\n                    )(PPh\n                    <jats:sub>3<\/jats:sub>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    ] (O\n                    <jats:sub>2<\/jats:sub>\n                    Cisoq = isoquinoline-1-carboxylate), characterized by x-ray crystallography, was used as a precursor to three-center bonded complexes [Rh(O\n                    <jats:sub>2<\/jats:sub>\n                    Cisoq)(\u03b7\n                    <jats:sup>2<\/jats:sup>\n                    -HSnPh\n                    <jats:sub>3<\/jats:sub>\n                    )(PPh\n                    <jats:sub>3<\/jats:sub>\n                    )(4-Rpy)] (R = carbomethoxy, acyl, bromo, aldehyde, hydrogen, methoxy, dimethylamino), which were prepared\n                    <jats:italic>in situ<\/jats:italic>\n                    from the bis(phosphine) complex in dichloromethane by addition of the pyridine. Of two isomeric forms of [Rh(O\n                    <jats:sub>2<\/jats:sub>\n                    Cisoq)(\u03b7\n                    <jats:sup>2<\/jats:sup>\n                    -HSnPh\n                    <jats:sub>3<\/jats:sub>\n                    )(PPh\n                    <jats:sub>3<\/jats:sub>\n                    )(4-Rpy)], one, with 4-Rpy positioned\n                    <jats:italic>trans<\/jats:italic>\n                    to tin, is formed at 0\u00b0C; the other, with isoquinoline positioned\n                    <jats:italic>trans<\/jats:italic>\n                    to tin, is formed by partial (25\u201350%) conversion of the first isomer (in solution) upon warming to 30\u201335\u00b0C for a few minutes. The relative coordination geometries of the two isomers were established by using a\n                    <jats:sup>15<\/jats:sup>\n                    N-enriched pyridine. NMR parameters (\n                    <jats:sup>1<\/jats:sup>\n                    H,\n                    <jats:sup>31<\/jats:sup>\n                    P,\n                    <jats:sup>103<\/jats:sup>\n                    Rh, and\n                    <jats:sup>119<\/jats:sup>\n                    Sn) for the pyridine-containing complexes show trends consistent with a significantly greater SnH interaction in complexes having isoquinoline lying\n                    <jats:italic>trans<\/jats:italic>\n                    to tin and a threshold of \u03c3 donor strength for the pyridine below which the influence on Rh(SnH) bonding is minimal and above which the influence is to enhance the SnH interaction. Possible reasons for these effects are discussed.\n                  <\/jats:p>","DOI":"10.1073\/pnas.0609697104","type":"journal-article","created":{"date-parts":[[2007,3,27]],"date-time":"2007-03-27T23:41:55Z","timestamp":1175038915000},"page":"6969-6973","update-policy":"https:\/\/doi.org\/10.1073\/pnas.cm10313","source":"Crossref","is-referenced-by-count":23,"title":["An NMR study of\n                    <i>trans<\/i>\n                    ligand influence in rhodium \u03b7\n                    <sup>2<\/sup>\n                    triphenyltin hydride complexes"],"prefix":"10.1073","volume":"104","author":[{"given":"Laurence","family":"Carlton","sequence":"first","affiliation":[{"name":"Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg, Republic of South Africa"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Manuel A.","family":"Fernandes","sequence":"additional","affiliation":[{"name":"Molecular Sciences Institute, 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