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In most cases, their phosphorus atoms are bound to heteroatoms such as oxygen or nitrogen (PN<jats:sub>3<\/jats:sub> or PN<jats:sub>2<\/jats:sub>O), whereas homoleptic coordination by three sp<jats:sup>2<\/jats:sup>\u2010hybridized carbon atoms has been reported only recently. Steric strain causes unique reactivity. Oxidative addition of halogens, N\u2212H or O\u2212H bonds have afforded phosphoranes as valuable materials for secondary processes. Ring opening was identified as an important step for the understanding of these reactions and has been observed experimentally with a diphosphorus\u2010based ring system. A PH<jats:sub>2<\/jats:sub> derivative has been considered as a model system for small molecule activation, and hydrogen transfer to a diazo compound was observed experimentally. Several of these phosphines are excellent ligands for the coordination of transition\u2010metal atoms. The very bulky PC<jats:sub>3<\/jats:sub> compound has a basicity similar to that of PPh<jats:sub>3<\/jats:sub> and may allow the synthesis of complexes with unusually low coordination numbers at the metal atoms. These phosphines found recently renewed interest as promising reagents in various secondary transformations such as the activation of \u03c3\u2010bonds or in coordination chemistry.<\/jats:p>","DOI":"10.1002\/chem.201803331","type":"journal-article","created":{"date-parts":[[2018,8,22]],"date-time":"2018-08-22T10:57:41Z","timestamp":1534935461000},"page":"1391-1404","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":50,"title":["Sterically Constrained Bicyclic Phosphines: A Class of Fascinating Compounds Suitable for Application in Small Molecule Activation and Coordination Chemistry"],"prefix":"10.1002","volume":"25","author":[{"given":"Alexander","family":"Brand","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Anorganische und Analytische Chemie Westf\u00e4lische Wilhelms-Universit\u00e4t M\u00fcnster  Corrensstrasse 30 48149 M\u00fcnster Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7178-5517","authenticated-orcid":false,"given":"Werner","family":"Uhl","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische und Analytische Chemie Westf\u00e4lische Wilhelms-Universit\u00e4t M\u00fcnster  Corrensstrasse 30 48149 M\u00fcnster Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2018,11,26]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/cs9972600345"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1039\/b503688g"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/om981033e"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0065-3055(04)52001-4"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.6b02911"},{"key":"e_1_2_7_7_1","unstructured":"\u00a0"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja301042u"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/om200017h"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100216y"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar2001759"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/tcr.201100016"},{"key":"e_1_2_7_13_1","unstructured":"\u00a0"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1141474"},{"key":"e_1_2_7_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar5003494"},{"key":"e_1_2_7_16_1","unstructured":"\u00a0"},{"key":"e_1_2_7_17_2","volume-title":"Frustrated Lewis Pairs, Vol.\u2005I, II of Topics in Current Chemistry","year":"2013"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200903708"},{"key":"e_1_2_7_18_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200903708"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201409800"},{"key":"e_1_2_7_19_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201409800"},{"key":"e_1_2_7_20_1","unstructured":"\u00a0"},{"key":"e_1_2_7_21_2","first-page":"101","volume-title":"Topics in Current Chemistry, Vol.\u2005334","author":"Uhl W.","year":"2013"},{"key":"e_1_2_7_22_2","first-page":"379","volume-title":"Organoaluminum compounds and Lewis pairs; 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