?url_ver=Z39.88-2004&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Adc&rft.relation=http%3A%2F%2Fd-scholarship-dev.library.pitt.edu%2F34993%2F&rft.title=New+Boron%E2%80%93Hydrogen+Insertion+Reactions+of+Ligated+Boranes&rft.creator=Allen%2C+Thomas&rft.description=Chemical+transformations+of+ligated+borane+complexes%2C+including+N-heterocyclic+carbene+boranes%2C+are+demonstrated.+Chapter+1+begins+with+an+introduction+of+Lewis+base+borane+complexes%2C+rhodium+carbene+chemistry%2C+and+B%E2%80%93H+insertion+of+ligated+boranes.+The+second+part+of+Chapter+1+describes+the+insertion+of+rhodium+carbenes%2C+previously+demonstrated+with+NHC-boranes%2C+into+the+B%E2%80%93H+bonds+of+other+ligated+boranes.+Stable+ligated+%CE%B1-boryl+esters+were+isolated.+A+series+of+competitive+B%E2%80%93H+insertion+experiments+are+described+that+were+used+to+develop+a+relative+reactivity+profile+of+ligated+boranes+toward+rhodium-catalyzed+B%E2%80%93H+insertion.+The+enantioselective+B%E2%80%93H+insertion+of+NHC-boranes+with+chiral+dirhodium+catalysts+was+also+investigated.+Finally%2C+the+synthesis+and+application+of+two+chiral+bridged+dirhodium+catalysts+is+described.%0D%0A%09Chapter+2+describes+the+discovery+and+isolation+of+NHC-boryl+hydrazones+by+non-chain+radical+recombinations+of+NHC-boranes%2C+diazomalonates%2C+and+azo+initiators.+Thermal+1%2C1-hydroborations+of+a+diazo+dione+and+a+diazonium+salt+to+give+boryl+hydrazone+and+boryl+diazene+products+are+demonstrated.+Chapter+3+explores+the+use+of+electrophilic+NHC-borane+complexes+to+catalyze+B%E2%80%93H+insertion+reactions+with+diazoesters.+The+boryl+iodide+catalyzed+method+is+adept+at+producing+%CE%B1-substituted-%CE%B1-NHC-boryl+esters.+A+small+family+of+NHC-boryl+esters+with+amino+acid+side+chains+was+synthesized.+Chapter+4+describes+the+basic+hydrolyses+of+ligated+%CE%B1-boryl+esters+to+yield+ligated+%CE%B1-boryl+acetic+acids.+The+boryl+acetic+acid+derivatives+were+characterized+by+X-ray+crystallography+and+acidity+constant+measurements.+They+are+among+the+least+acidic+carboxylic+acids+known.+The+electron-donating+ability+of+ligated+borane+substituents+was+further+quantified+by+using+derived+Hammett+constants+from+13C+NMR+chemical+shift+correlation+experiments.&rft.date=2018-09-26&rft.type=University+of+Pittsburgh+ETD&rft.type=PeerReviewed&rft.format=application%2Fpdf&rft.language=en&rft.identifier=http%3A%2F%2Fd-scholarship-dev.library.pitt.edu%2F34993%2F1%2Fallenth_PittETD2018_1.pdf&rft.identifier=++Allen%2C+Thomas++(2018)+New+Boron%E2%80%93Hydrogen+Insertion+Reactions+of+Ligated+Boranes.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++