{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,1]],"date-time":"2026-10-01T14:18:47Z","timestamp":1790864327731,"version":"4.1.0"},"reference-count":58,"publisher":"Wiley","issue":"45","license":[{"start":{"date-parts":[[2011,10,4]],"date-time":"2011-10-04T00:00:00Z","timestamp":1317686400000},"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":[[2011,11,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The puzzling question of alkyne insertion into Pd\uf8ffP and Pd\uf8ffH bonds leading to the formation of new Pd\uf8ffC, C\uf8ffP, and C\uf8ffH bonds was explored by theoretical calculations at the CCSD(T) and B3LYP levels of theory. The key factors responsible for selectivity of catalytic hydrofunctionalization of alkynes were resolved and studied in details for the models of hydrophosphorylation, hydrophosphinylation, and hydrophospination reactions. In contrast with the generally accepted mechanistic picture, the calculations have shown that several pathways are possible depending on the nature and geometrical arrangement of the phosphorus group. It was found that the product of alkyne insertion into the metal\u2013hydrogen bond should be easily formed under kinetic\u2010control conditions, while the product of alkyne insertion into the metal\u2013phosphorus bond may be formed in certain cases under thermodynamic control. For the first time, the calculations have revealed the role of the oxygen atom in the reactivity of P=P(O)R<jats:sub>2<\/jats:sub> groups and the role of the interactions involving the lone pair of the P=PR<jats:sub>2<\/jats:sub> group in the reagent. The fundamental properties of the Pd\uf8ffP, C\uf8ffP, and P\uf8ffH bonds were reported, and the larger bond strength upon increasing the number of oxygen atoms bound to phosphorus (P=PR<jats:sub>2<\/jats:sub>, P(O)R<jats:sub>2<\/jats:sub>, and P(O)(OR)<jats:sub>2<\/jats:sub>) have been shown. The relationship between bond energy, acidity, and reactivity of the studied phosphorus compounds has been determined.<\/jats:p>","DOI":"10.1002\/chem.201101898","type":"journal-article","created":{"date-parts":[[2011,10,4]],"date-time":"2011-10-04T04:33:11Z","timestamp":1317702791000},"page":"12623-12630","source":"Crossref","is-referenced-by-count":34,"title":["Catalytic Hydrofunctionalization of Alkynes through P\uf8ffH Bond Addition: The Unique Role of Orientation and Properties of the Phosphorus Group in the Insertion Step"],"prefix":"10.1002","volume":"17","author":[{"given":"Valentine P.","family":"Ananikov","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anton V.","family":"Makarov","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Irina P.","family":"Beletskaya","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2011,10,4]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9000644"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1098\/rspa.2009.0558"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.2174\/138527208785909600"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar7001655"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr0306788"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200300616"},{"key":"e_1_2_6_8_2","volume-title":"Catalytic Heterofunctionalization: From Hydroamination to Hydrozirconization","year":"2001"},{"key":"e_1_2_6_9_2","volume-title":"Phosphorus Compounds: Advanced Tools in Catalysis and Material Sciences","year":"2011"},{"key":"e_1_2_6_10_2","unstructured":"\u00a0"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-642-12073-2_4"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1007\/b13778"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.200800331"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.2174\/138527205774913079"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2010.08.043"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201000792"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/om8008298"},{"key":"e_1_2_6_18_2","unstructured":"Protonolysis or \u03c3\u2010bond metathesis may be also involved after alkyne insertion see Ref.\u2005[3] for details."},{"key":"e_1_2_6_19_2","unstructured":"\u00a0"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/asia.201000840"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201000606"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1134\/S1070428010090010"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-0029-1217739"},{"key":"e_1_2_6_24_2","unstructured":"TheVII\u2192X\u2010TSactivation barrier is 1\u2005kcal\u2009mol\u22121on the \u0394Esurface (Table S1 in the Supporting Information) which vanished on the \u0394Gsurface owing to approximate calculations of free\u2010energy corrections."},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2007.12.023"},{"key":"e_1_2_6_26_2","unstructured":"The calculated value of activation energy for pyramidal inversion of the phosphorus center involving P=P(O)R2groups was >50\u2005kcal\u2009mol\u22121 thus making the process hardly possible under regular experimental conditions."},{"key":"e_1_2_6_27_2","unstructured":"For accuracy of DFT methods for structure optimizations and improvements with single point calculations see:"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1039\/b907148b"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.molcata.2010.03.015"},{"key":"e_1_2_6_30_2","unstructured":"The same bond energies were calculated for complexVIIas well; see Tables S7 in the Supporting Information."},{"key":"e_1_2_6_31_2","unstructured":"The calculatedtrans\u2010influence changed in the order: P=PMe2> P(O)Me2> P(O)(OMe)2."},{"key":"e_1_2_6_32_2","unstructured":"It should be pointed out that BDE (Pd\uf8ffP)>BDE (Pd\uf8ffH) at the CCSD(T) level whereas this is not the case at the B3LYP level (see Tables S5 and S6 in the Supporting Information). However at both CCSD(T) and B3LYP levels the same relative tendency for the P=PMe2 P(O)Me2 and P(O)(OMe)2groups was calculated."},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2006.02.049"},{"key":"e_1_2_6_34_2","unstructured":"J.\u2005E. Bartmess \u201cNegative Ion Energetics Data\u201d inNIST Chemistry WebBook NIST Standard Reference Database Number 69(Eds.: P.\u2005J. Linstrom W.\u2005G. Mallard) National Institute of Standards and Technology Gaithersburg http:\/\/webbook.nist.gov (retrieved June 21 2011);"},{"key":"e_1_2_6_35_2","volume-title":"Nucleophilicity","author":"McDonald R. 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Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman J.\u2005A. Montgomery Jr. T. Vreven K.\u2005N. Kudin J.\u2005C. Burant J.\u2005M. Millam S.\u2005S. Iyengar J. Tomasi V. Barone B. Mennucci M. Cossi G. Scalmani N. Rega G.\u2005A. Petersson H. Nakatsuji M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai M. Klene X. Li J.\u2005E. Knox H.\u2005P. Hratchian J.\u2005B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski P.\u2005Y. Ayala K. Morokuma G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg V.\u2005G. Zakrzewski S. Dapprich A.\u2005D. Daniels M.\u2005C. Strain O. Farkas D.\u2005K. Malick A.\u2005D. Rabuck K. Raghavachari J.\u2005B. Foresman J.\u2005V. Ortiz Q. Cui A.\u2005G. Baboul S. Clifford J. Cioslowski B.\u2005B. Stefanov G. Liu A. Liashenko P. Piskorz I. Komaromi R.\u2005L. Martin D.\u2005J. Fox T. Keith M.\u2005A. Al\u2010Laham C.\u2005Y. Peng A. Nanayakkara M. Challacombe P.\u2005M.\u2005W. Gill B. Johnson W. Chen M.\u2005W. Wong C. Gonzalez J.\u2005A. Pople Gaussian Inc. 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