{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,4]],"date-time":"2026-10-04T02:11:29Z","timestamp":1791079889447,"version":"4.1.0"},"reference-count":104,"publisher":"Wiley","issue":"7","license":[{"start":{"date-parts":[[2011,1,17]],"date-time":"2011-01-17T00:00:00Z","timestamp":1295222400000},"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":[[2011,2,11]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:italic>O<\/jats:italic>,<jats:italic>O<\/jats:italic>\u2032\u20103,3\u2032\u2010Di\u2010<jats:italic>tert<\/jats:italic>\u2010butyl\u20105,5\u2032\u2010dimethoxy\u20101,1\u2032\u2010biphenyl\u20102,2\u2032\u2010diyl phosphonate (<jats:bold>1<\/jats:bold>) is the hydrolysis product of several mono\u2010 and bis\u2010phosphites used as ligands in industrial hydroformylation and other catalytic reactions. As a result of a tautomeric equilibrium, this pentavalent heteroatom\u2010substituted phosphine oxide (HASPO) can rearrange to the corresponding trivalent phosphorus compound. The latter is able to react with typical rhodium\u2010containing precursors frequently used for the generation of catalysts. The resulting species were characterised by NMR spectroscopy and X\u2010ray structure analysis. Proof is given that a rhodium complex of <jats:bold>1<\/jats:bold> forms an active hydroformylation catalyst. Moreover, <jats:bold>1<\/jats:bold> can add to aldehydes, which are generated as products in the hydroformylation. Thus a broad range of subsequent reactions can be associated with the degradation of the original phosphite ligands, which has a strong influence on the overall outcome of the hydroformylation reaction.<\/jats:p>","DOI":"10.1002\/chem.201002823","type":"journal-article","created":{"date-parts":[[2011,1,17]],"date-time":"2011-01-17T10:42:19Z","timestamp":1295260939000},"page":"2120-2129","source":"Crossref","is-referenced-by-count":46,"title":["Heteroatom\u2010Substituted Secondary Phosphine Oxides (HASPOs) as Decomposition Products and Preligands in Rhodium\u2010Catalysed Hydroformylation"],"prefix":"10.1002","volume":"17","author":[{"given":"Andrea","family":"Christiansen","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Detlef","family":"Selent","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anke","family":"Spannenberg","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Martin","family":"K\u00f6ckerling","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Helmut","family":"Reinke","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wolfgang","family":"Baumann","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Haijun","family":"Jiao","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Robert","family":"Franke","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Armin","family":"B\u00f6rner","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2011,1,17]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"For reviews see:"},{"key":"e_1_2_6_2_2","first-page":"201","volume-title":"Catalysis: An Integrated Approach to Homogeneous, Heterogeneous and Industrial Catalysis","author":"Leeuwen P. 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G.Abatjoglou D. R.Bryant US 4769498 1987;"},{"key":"e_1_2_6_36_3","unstructured":"E.Billig A. G.Abatjoglou D. R.Bryant US 4668651 1985;"},{"key":"e_1_2_6_36_4","unstructured":"E.Billig A. G.Abatjoglou D. R.Bryant US 4748261 1985;"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00058a079"},{"key":"e_1_2_6_38_2","unstructured":"R.Li C.Lai Y.Pan W.Shan W.Jiang CN 101288852A20081022;"},{"key":"e_1_2_6_39_2","unstructured":"T. C.Eisenschmid R. R.Peterson G. A.Miller A. G.Abatjoglou WO 2008115740A1;"},{"key":"e_1_2_6_40_2","unstructured":"D.Selent A.B\u00f6rner B.Kreidler D.Hess K.\u2010D.Wiese WO 2008071508A120080619;"},{"key":"e_1_2_6_41_2","unstructured":"H.Guo L.Zhu H.Wang T.Bao Y.Wang CN 101565353A20091028;"},{"key":"e_1_2_6_42_2","unstructured":"Y.Pan C.Lai R.Li W.Shan CN 101332437A20081231;"},{"key":"e_1_2_6_43_2","unstructured":"W.\u2010J.Peng C. L.Rand WO 2008134326A120081106;"},{"key":"e_1_2_6_44_2","unstructured":"T. C.Eisenschmid R. P.Peterson G. A.Miller A. G.Abatjoglou WO 2008115740A120080925;"},{"key":"e_1_2_6_45_2","unstructured":"K.Ding X.Peng Z.Wang J.Wu CN 101768060A20100707."},{"key":"e_1_2_6_46_2","unstructured":"For mechanistic investigations of the hydroformylation reaction with this type of ligand see:"},{"key":"e_1_2_6_47_2","doi-asserted-by":"publisher","DOI":"10.1039\/b105391b"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.200300296"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.200900292"},{"key":"e_1_2_6_50_2","unstructured":"For some recent examples see:"},{"key":"e_1_2_6_51_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200903350"},{"key":"e_1_2_6_52_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200902777"},{"key":"e_1_2_6_53_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.200900911"},{"key":"e_1_2_6_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja904152r"},{"key":"e_1_2_6_55_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.200801093"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1039\/b806891g"},{"key":"e_1_2_6_57_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200600654"},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200701636"},{"key":"e_1_2_6_59_2","unstructured":"DFT calculations on related HASPOs gave evidence that the equilibrium is strongly dependent on the electronic effects of aryl substituents. 1 1\u2032\u2010Biphenyl\u20102 2\u2032\u2010diyl phosphonate: ratio ofB\/C=43:57 (\u0394G=0.17\u2005kcal\u2009mol\u22121); 3 3\u2032 5 5\u2032\u2010tetrafluoro\u20101 1\u2032\u2010biphenyl\u20102 2\u2032\u2010diyl phosphonate: ratio ofB\/C=5:95 (\u0394G=1.81\u2005kcal\u2009mol\u22121); 3 3\u2032 5 5\u2032\u2010tetrakis(trifluoromethyl)\u20101 1\u2032\u2010biphenyl\u20102 2\u2032\u2010diyl phosphonate: ratio ofB\/C=1:99 (\u0394G=3.49\u2005kcal\u2009mol\u22121)."},{"key":"e_1_2_6_60_2","doi-asserted-by":"publisher","DOI":"10.1039\/B716389D"},{"key":"e_1_2_6_61_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50149a065"},{"key":"e_1_2_6_62_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0204686"},{"key":"e_1_2_6_63_2","doi-asserted-by":"publisher","DOI":"10.1039\/DT9960004357"},{"key":"e_1_2_6_64_2","unstructured":"For related \u201chead\u2010to\u2010head\u201d binuclear complexes see:"},{"key":"e_1_2_6_65_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00281a008"},{"key":"e_1_2_6_66_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19821150522"},{"key":"e_1_2_6_67_2","unstructured":"X\u2010ray diffraction on crystals of7withn\u2010heptane in the lattice gave a unit cell isomorphous with that from7with CH2Cl2in the lattice obtained by Faraone and co\u2010workers.[19]Crystallographic data for7can be obtained from the authors on request."},{"key":"e_1_2_6_68_2","unstructured":"\u00a0"},{"key":"e_1_2_6_69_2","doi-asserted-by":"publisher","DOI":"10.1107\/S1600536804013406"},{"key":"e_1_2_6_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/om061065z"},{"key":"e_1_2_6_71_2","unstructured":"The \u03b76coordination mode was evidenced by a preliminary X\u2010ray structural analysis."},{"key":"e_1_2_6_72_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20020301)114:5<814::AID-ANGE814>3.0.CO;2-J"},{"key":"e_1_2_6_72_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020301)41:5<777::AID-ANIE777>3.0.CO;2-7"},{"key":"e_1_2_6_73_2","unstructured":"For related BF2\u2010bridged complexes see:"},{"key":"e_1_2_6_74_2","doi-asserted-by":"publisher","DOI":"10.1039\/dt9840000801"},{"key":"e_1_2_6_75_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(90)85067-9"},{"key":"e_1_2_6_76_2","unstructured":"Remarkably only a single example of a mononuclear rhodium complex has been described up to now. The [Rh(CO)2(PR2O)2BF2] complex was isolated in a yield of only 30\u2009% whereas similar complexes with metals other than rhodium could be prepared in yields of >75\u2009%.[18]"},{"key":"e_1_2_6_77_2","doi-asserted-by":"publisher","DOI":"10.1021\/om9807093"},{"key":"e_1_2_6_78_2","first-page":"130","volume":"51","author":"Ustynyuk Yu. A.","year":"2007","journal-title":"Ross. Khim. Zh."},{"key":"e_1_2_6_79_2","unstructured":"Because GC samples were only taken after 4\u2005hours of reaction time this ligand\u2010enhancing activity effect is only reflected in the gas consumption curves and is not evident in Table\u20051."},{"key":"e_1_2_6_80_2","unstructured":"E.Billig A. G.Abatjoglou D. R.Bryant R. E.Murray J. M.Maher US 4789753 1987."},{"key":"e_1_2_6_81_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1979-28566"},{"key":"e_1_2_6_82_2","volume-title":"Synthesis of Carbon\u2010Phosphorus Bonds","author":"Engel R.","year":"1987"},{"key":"e_1_2_6_83_2","unstructured":"See also:M.Takai I.Nakajima T.Tsukahara Y.Tanaka H.Urata A.Nakanishi EP 1008581B1 2004."},{"key":"e_1_2_6_84_2","unstructured":"This reversibility has already been mentioned by:"},{"key":"e_1_2_6_85_2","volume-title":"Synthesis of Carbon\u2010Phosphorus Bonds","author":"Engel R.","year":"1987"},{"key":"e_1_2_6_86_2","first-page":"244","volume-title":"Phosphorverbindungen in Houben\u2013Weyl, Methoden der Organischen Chemie, Vol.\u2005E1","author":"Kleiner H.\u2010J.","year":"1982"},{"key":"e_1_2_6_87_2","unstructured":"The addition of (HA)SPOs to olefins can be mediated for example by bases acids radical initiators and transition metals:"},{"key":"e_1_2_6_88_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol062505l"},{"key":"e_1_2_6_89_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200606045"},{"key":"e_1_2_6_90_2","unstructured":"Recently Garland and Pringle suggested subunits of phosphinite ligands which may be resistant towards hydrolysis: M.\u2005C. Garland P.\u2005G. Pringle 17. International Symposium on Homogeneous Catalysis Poznan (Poland) 2010 Abstractbook p.\u2005158 Poster P\u201082."},{"key":"e_1_2_6_91_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108767307043930"},{"key":"e_1_2_6_92_2","doi-asserted-by":"publisher","DOI":"10.1107\/S002188980403225X"},{"key":"e_1_2_6_93_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20010504)113:9<1739::AID-ANGE17390>3.0.CO;2-5"},{"key":"e_1_2_6_93_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010504)40:9<1696::AID-ANIE16960>3.0.CO;2-2"},{"key":"e_1_2_6_94_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50003a061"},{"key":"e_1_2_6_95_2","unstructured":"Gaussian\u200503 Revision D.02 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman J.\u2005A. Montgomery \u2005Jr. T. Vreven K.\u2005N. Kudin J.\u2005C. Burant J.\u2005M. Millam S.\u2005S. Iyengar J. Tomasi V. Barone B. Mennucci M. Cossi G. 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Wallingford CT 2004."},{"key":"e_1_2_6_96_2","unstructured":"XP\u2014Interactive Molecular Graphics Version\u20055.1 Bruker AXS Inc. Madison WI (USA) 1998."},{"key":"e_1_2_6_97_2","unstructured":"K. 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