{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,1]],"date-time":"2026-03-01T08:53:07Z","timestamp":1772355187890,"version":"3.50.1"},"reference-count":39,"publisher":"Wiley","issue":"52","license":[{"start":{"date-parts":[[2011,12,6]],"date-time":"2011-12-06T00:00:00Z","timestamp":1323129600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2011,12,23]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Secondary phosphane oxides, R<jats:sub>2<\/jats:sub>P(O)H, are commonly used as preligands for transition\u2010metal complexes of phosphinous acids, R<jats:sub>2<\/jats:sub>P\uf8ffOH (R=alkyl, aryl), which are relevant as efficient catalysts in cross\u2010coupling processes. In contrast to previous work by other groups, we are interested in the ligating properties of an electron\u2010deficient phosphinous acid, (R<jats:sub>f<\/jats:sub>)<jats:sub>2<\/jats:sub>P\uf8ffOH, bearing the strongly electron\u2010withdrawing and sterically demanding 2,4\u2010bis(trifluoromethyl)phenyl group towards catalysis\u2010relevant metals, such as palladium and platinum. The preligand bis[2,4\u2010bis(trifluoromethyl)phenyl]phosphane oxide, (R<jats:sub>f<\/jats:sub>)<jats:sub>2<\/jats:sub>P(O)H, reacts smoothly with solid platinum(II) dichloride yielding the <jats:italic>trans<\/jats:italic>\u2010configured phosphinous acid platinum complex <jats:italic>trans<\/jats:italic>\u2010[PtCl<jats:sub>2<\/jats:sub>({2,4\u2010(CF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>POH)<jats:sub>2<\/jats:sub>]. The deprotonation of one phosphinous acid ligand with an appropriate base leads to the <jats:italic>cis<\/jats:italic>\u2010configured monoanion complex <jats:italic>cis<\/jats:italic>\u2010[PtCl<jats:sub>2<\/jats:sub>({2,4\u2010(CF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>\u2010 PO)<jats:sub>2<\/jats:sub>H]<jats:sup>\u2212<\/jats:sup>, featuring the quasi\u2010chelating phosphinous acid phosphinito unit, (R<jats:sub>f<\/jats:sub>)<jats:sub>2<\/jats:sub>P\uf8ffO\uf8ffH\u22c5\u22c5\u22c5O\uf8feP(R<jats:sub>f<\/jats:sub>)<jats:sub>2<\/jats:sub>, which exhibits a strong hydrogen bridge substantiated by an O\u22c5\u22c5\u22c5O distance of 245.1(4)\u2005pm. The second deprotonation step is accompanied by a rearrangement to afford the <jats:italic>trans<\/jats:italic>\u2010configured dianion <jats:italic>trans<\/jats:italic>\u2010[PtCl<jats:sub>2<\/jats:sub>({2,4\u2010(CF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>PO)<jats:sub>2<\/jats:sub>]<jats:sup>2\u2212<\/jats:sup>. The reaction of (R<jats:sub>f<\/jats:sub>)<jats:sub>2<\/jats:sub>P(O)H with solid palladium(II) dichloride initially yields a mononuclear palladium complex [PdCl<jats:sub>2<\/jats:sub>({2,4\u2010(CF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>POH)<jats:sub>2<\/jats:sub>], which condenses under liberation of HCl to the neutral dinuclear palladium complex [Pd<jats:sub>2<\/jats:sub>(\u03bc\u2010Cl)<jats:sub>2<\/jats:sub>{({2,4\u2010(CF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>PO)<jats:sub>2<\/jats:sub>H}<jats:sub>2<\/jats:sub>]. The equilibrium between the mononuclear [PdCl<jats:sub>2<\/jats:sub>({2,4\u2010(CF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>POH)<jats:sub>2<\/jats:sub>] and dinuclear [Pd<jats:sub>2<\/jats:sub>(\u03bc\u2010Cl)<jats:sub>2<\/jats:sub>{({2,4\u2010(CF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>PO)<jats:sub>2<\/jats:sub>H}<jats:sub>2<\/jats:sub>] palladium complexes is reversible and can be shifted in each direction by the addition of base or HCl, respectively. Treatment of palladium(II) hexafluoroacetylacetonate, [Pd(F<jats:sub>6<\/jats:sub>acac)<jats:sub>2<\/jats:sub>], with a slight excess of (R<jats:sub>f<\/jats:sub>)<jats:sub>2<\/jats:sub>P(O)H yields the complex [Pd(F<jats:sub>6<\/jats:sub>acac)({2,4\u2010(CF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>\u2010 PO)<jats:sub>2<\/jats:sub>H]. The quasi\u2010chelating phosphinous acid phosphinito unit, which is formed by the liberation of HF<jats:sub>6<\/jats:sub>acac, is characterized by a O\u22c5\u22c5\u22c5O distance of 244.1(3)\u2005pm. These transition metal complexes are stable towards air and moisture and can be stored for months without any evidence of decomposition.<\/jats:p>","DOI":"10.1002\/chem.201102347","type":"journal-article","created":{"date-parts":[[2011,12,6]],"date-time":"2011-12-06T10:21:51Z","timestamp":1323166911000},"page":"14935-14941","source":"Crossref","is-referenced-by-count":14,"title":["Air\u2010Stable Platinum and Palladium Complexes Featuring Bis[2,4\u2010bis(trifluoromethyl)phenyl]phosphinous Acid Ligands"],"prefix":"10.1002","volume":"17","author":[{"given":"Boris","family":"Kurscheid","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Beate","family":"Neumann","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hans\u2010Georg","family":"Stammler","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Berthold","family":"Hoge","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2011,12,6]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-2006-926427"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200460848"},{"key":"e_1_2_6_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200460848"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/om100171p"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201007992"},{"key":"e_1_2_6_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201007992"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol100658y"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100244e"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr1002497"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100218m"},{"key":"e_1_2_6_10_2","unstructured":"For examples of phosphane catalysts see:"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201000267"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19981217)110:24<3586::AID-ANGE3586>3.0.CO;2-7"},{"key":"e_1_2_6_12_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19981231)37:24<3387::AID-ANIE3387>3.0.CO;2-P"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19990816)111:16<2568::AID-ANGE2568>3.0.CO;2-J"},{"key":"e_1_2_6_13_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19990816)38:16<2411::AID-ANIE2411>3.0.CO;2-T"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0002058"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo9820059"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo062452l"},{"key":"e_1_2_6_17_2","unstructured":"For examples of phosphinous acid transition\u2010metal complexes see:"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol802642g"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-2003-41018"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo010764c"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/j19680002745"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01491a062"},{"key":"e_1_2_6_22_3","doi-asserted-by":"publisher","DOI":"10.1021\/ja00877a005"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200801837"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201100984"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2004.09.041"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201000037"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.200700140"},{"key":"e_1_2_6_28_2","unstructured":"\u00a0"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/om100602j"},{"key":"e_1_2_6_30_2","first-page":"8620","volume":"39","author":"Waddel P. 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