{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T04:37:55Z","timestamp":1789533475410,"version":"build-2803163510"},"reference-count":75,"publisher":"Wiley","issue":"7","license":[{"start":{"date-parts":[[2009,1,2]],"date-time":"2009-01-02T00:00:00Z","timestamp":1230854400000},"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":[[2009,2,2]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    <jats:bold>Unprecedented C\uf8ffP systems<\/jats:bold>\n                    : Me\n                    <jats:sub>3<\/jats:sub>\n                    SiX (X=Br, I) catalyses rearrangements of P\n                    <jats:sup>III<\/jats:sup>\n                    esters R\u2032R\u2032\u2032P\uf8ffOR into the corresponding phosphoryl systems, providing a simple, mild and efficient route to a variety of structures containing P\uf8ffC bonds. The mechanism has been found to be fundamentally different from that of the Arbuzov\u2013Michaelis reaction and includes three definite steps a, b and c (see scheme).\n                    <jats:boxed-text content-type=\"graphic\" position=\"anchor\">\n                      <jats:graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" mimetype=\"image\/gif\" position=\"anchor\" specific-use=\"enlarged-web-image\" xlink:href=\"graphic\/mcontent.gif\">\n                        <jats:alt-text>magnified image<\/jats:alt-text>\n                      <\/jats:graphic>\n                    <\/jats:boxed-text>\n                  <\/jats:p>\n                  <jats:p>\n                    Halotrimethylsilanes Me\n                    <jats:sub>3<\/jats:sub>\n                    SiX (X=Br, I) catalyse rearrangements of tricoordinate phosphorus esters R\u2032R\u2032\u2032P\uf8ffOR into the corresponding phosphoryl systems R\u2032R\u2032\u2032P(O)R. This provides a simple and efficient route to a variety of structures containing phosphorus\uf8ffcarbon bonds, under mild conditions and with good yields. The reaction mechanism was investigated in detail by\n                    <jats:sup>31<\/jats:sup>\n                    P\u2005NMR spectroscopy and independent synthesis of the reaction intermediates. It has been demonstrated that the primary products of this catalytic reaction are halogeno P\n                    <jats:sup>III<\/jats:sup>\n                    structures R\u2032R\u2032\u2032PX and silyl ethers ROSiMe\n                    <jats:sub>3<\/jats:sub>\n                    and that they subsequently react to give the corresponding phosphorus silyl esters\u2014Me\n                    <jats:sub>3<\/jats:sub>\n                    SiOPR\u2032R\u2032\u2032\u2014and alkyl halides RX. At higher temperatures these intermediates then react to form R\u2032R\u2032\u2032P(O)R compounds. This paper also features the surprising observation that when esters Ph\n                    <jats:sub>2<\/jats:sub>\n                    POR and halotrimethylsilanes Me\n                    <jats:sub>3<\/jats:sub>\n                    SiX (X=Br, I) are used in 2:1 ratio, phosphonium salts Ph\n                    <jats:sub>2<\/jats:sub>\n                    R\n                    <jats:sub>2<\/jats:sub>\n                    P\n                    <jats:sup>+<\/jats:sup>\n                    X\n                    <jats:sup>\u2212<\/jats:sup>\n                    and trimethylsilyl diphenylphosphinate\u2014Ph\n                    <jats:sub>2<\/jats:sub>\n                    P(O)OSiMe\n                    <jats:sub>3<\/jats:sub>\n                    \u2014are formed as the major products. Experimental evidence indicates that the mechanisms of both reactions are fundamentally different from that of the Michaelis\u2013Arbuzov reaction. Me\n                    <jats:sub>3<\/jats:sub>\n                    SiCl is not reactive and this paper explains why.\n                  <\/jats:p>","DOI":"10.1002\/chem.200800435","type":"journal-article","created":{"date-parts":[[2009,1,2]],"date-time":"2009-01-02T20:16:21Z","timestamp":1230927381000},"page":"1747-1756","source":"Crossref","is-referenced-by-count":33,"title":["Studies on the Efficient Generation of Phosphorus\uf8ffCarbon Bonds via a Rearrangement of P\n                    <sup>III<\/sup>\n                    Esters Catalysed by Trimethylhalosilanes"],"prefix":"10.1002","volume":"15","author":[{"given":"Wojciech","family":"Dabkowski","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alfred","family":"Ozarek","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sebastian","family":"Olejniczak","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marek","family":"Cypryk","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Julian","family":"Chojnowski","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jan","family":"Michalski","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2009,1,26]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","volume-title":"A Guide To Organophosphorus Chemistry","author":"Louis D.","year":"2000"},{"key":"e_1_2_6_3_2","volume-title":"Studies in Inorganic Chemistry 6, Phosphorus: An Outline of its Chemistry Biochemistry and Technology","author":"Corbridge D. 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