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A mixture of the cyclic trimer [R<jats:sub>2<\/jats:sub>P\u2010BH<jats:sub>2<\/jats:sub>]<jats:sub>3<\/jats:sub> and tetramer [R<jats:sub>2<\/jats:sub>P\u2010BH<jats:sub>2<\/jats:sub>]<jats:sub>4<\/jats:sub> was obtained from the same reaction at a more elevated temperature of 100\u2009\u00b0C. The analogous rhodium\u2010catalyzed dehydrocoupling of the primary phosphine\u2013borane adduct RPH<jats:sub>2<\/jats:sub>\u22c5BH<jats:sub>3<\/jats:sub> at 60\u2009\u00b0C gave the high molecular weight polyphosphinoborane polymer [RPH\u2010BH<jats:sub>2<\/jats:sub>]<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub> (<jats:italic>M<\/jats:italic><jats:sub>w<\/jats:sub> = 56\u2009170, PDI = 1.67). The molecular weight was investigated by gel permeation chromatography and the compound characterized by multinuclear NMR spectroscopy. Interestingly, the electron\u2010withdrawing fluorinated aryl substituents have an important influence on the reactivity as the dehydrocoupling process occurred efficiently at the mildest temperatures observed for phosphine\u2013borane adducts to date. Thin films of polymeric [RPH\u2010BH<jats:sub>2<\/jats:sub>]<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub> (R = <jats:italic>p<\/jats:italic>\u2010CF<jats:sub>3<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>) have also been shown to function as effective negative\u2010tone resists towards electron beam (e\u2010beam) lithography (EBL). The resultant patterned bars were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and time\u2010of\u2010flight secondary ion mass spectrometry (TOF\u2010SIMS).<\/jats:p>","DOI":"10.1002\/chem.200401296","type":"journal-article","created":{"date-parts":[[2005,5,18]],"date-time":"2005-05-18T04:50:33Z","timestamp":1116391833000},"page":"4526-4534","source":"Crossref","is-referenced-by-count":122,"title":["Rhodium\u2010Catalyzed Dehydrocoupling of Fluorinated Phosphine\u2013Borane Adducts: Synthesis, Characterization, and Properties of Cyclic and Polymeric Phosphinoboranes with Electron\u2010Withdrawing Substituents at Phosphorus"],"prefix":"10.1002","volume":"11","author":[{"given":"Timothy J.","family":"Clark","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jos\u00e9 M.","family":"Rodezno","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Scott 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