{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T00:17:55Z","timestamp":1788394675463,"version":"build-2803163510"},"reference-count":45,"publisher":"Wiley","issue":"5","license":[{"start":{"date-parts":[[2007,3,29]],"date-time":"2007-03-29T00:00:00Z","timestamp":1175126400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry \u0097 An Asian Journal"],"published-print":{"date-parts":[[2007,5,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Trialkynylphosphines substituted with bulky triarylsilyl groups at the alkyne termini were synthesized. The new phosphines P(C\uf8fdCSiAr<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub> (Ar=3,5\u2010<jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>\u20104\u2010MeOC<jats:sub>6<\/jats:sub>H<jats:sub>2<\/jats:sub>, 3,5\u2010(Me<jats:sub>3<\/jats:sub>Si)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>) are uncrowded near the phosphorus atom but bulky in the distal region. As a result, they contain a large cavity, at the bottom of which the phosphine lone\u2010pair electrons are located. The compounds are stable to oxidation by air and hydrolysis. DFT calculations suggested that the triethynylphosphines are good \u03c0\u2010acceptor ligands, comparable with P(OAr)<jats:sub>3<\/jats:sub>. The trialkynylphosphines reacted with [{RhCl(cod)}<jats:sub>2<\/jats:sub>] (P\/Rh=1.1:1) to give selectively the monophosphine\u2013rhodium complex [RhCl(cod)P(C\uf8fdCSiAr<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>]. X\u2010ray crystal\u2010structure analysis revealed that the {RhCl(cod)} fragment is fully accommodated by the cavity of the phosphine ligand. Compared to the effect of analogues with smaller end caps and PPh<jats:sub>3<\/jats:sub>, the trialkynylphosphines accelerated markedly the rhodium\u2010catalyzed hydrosilylation of ketones with a triorganosilane. It is proposed that the higher catalytic activity observed with the holey phosphines is a result of the preferential formation of a monophosphine\u2013rhodium species.<\/jats:p>","DOI":"10.1002\/asia.200700006","type":"journal-article","created":{"date-parts":[[2007,3,29]],"date-time":"2007-03-29T06:18:50Z","timestamp":1175149130000},"page":"609-618","source":"Crossref","is-referenced-by-count":42,"title":["Phosphorus Ligands with a Large Cavity: Synthesis of Triethynylphosphines with Bulky End Caps and Application to the Rhodium\u2010Catalyzed Hydrosilylation of Ketones"],"prefix":"10.1002","volume":"2","author":[{"given":"Atsuko","family":"Ochida","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Masaya","family":"Sawamura","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2007,4,27]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"For the coordination of alkynyl phosphines through the phosphorus atom to a metal center see:"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50071a028"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2004.05.017"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00002a061"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja066800c"},{"key":"e_1_2_6_6_2","unstructured":"For multinuclear complexes see:"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/om970663y"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/om020052s"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/om000895o"},{"key":"e_1_2_6_10_2","unstructured":"For the reactivity of alkynylphosphines see:"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/recl.19700891008"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1977-24597"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00858a010"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(01)01074-9"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00076a022"},{"key":"e_1_2_6_16_2","unstructured":"\u00a0"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2002.346"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1080\/10426500213444"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200352616"},{"key":"e_1_2_6_19_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200352616"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic0109400"},{"key":"e_1_2_6_21_2","unstructured":"\u00a0"},{"key":"e_1_2_6_22_2","first-page":"2835","author":"Afanasiev V. 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