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Synthetic Routes to Metal Alkylidene Complexes that Catalyze Olefin Metathesis and the Utilization of [1.1.1]Propellane as a Carbene Precursor
Synthetic Routes to Metal Alkylidene Complexes that Catalyze Olefin Metathesis and the Uti...
Synthetic Routes to Metal Alkylidene Complexes that Catalyze Olefin Metathesis and the Utilization of [1.1.1]Propellane as a Carbene Precursor

Detailed Information

자료유형  
 학위논문 서양
최종처리일시  
20250211150908
ISBN  
9798384048510
DDC  
540
저자명  
George, Gregory.
서명/저자  
Synthetic Routes to Metal Alkylidene Complexes that Catalyze Olefin Metathesis and the Utilization of [1.1.1]Propellane as a Carbene Precursor
발행사항  
[Sl] : Cornell University, 2024
발행사항  
Ann Arbor : ProQuest Dissertations & Theses, 2024
형태사항  
202 p
주기사항  
Source: Dissertations Abstracts International, Volume: 86-03, Section: B.
주기사항  
Advisor: Wolczanski, Peter.
학위논문주기  
Thesis (Ph.D.)--Cornell University, 2024.
초록/해제  
요약Olefin metathesis is a class of reactions utilized in the fine-chemical and commodities industries. Homogenous catalysis of olefin metathesis can be performed by metal alkylidene species, and these compounds have been investigated for decades. In recent years, a focus has been placed on the development of catalysts using metals with lower toxicity and cost when compared to original systems utilizing ruthenium and molybdenum.The purpose of this work is to explore alternative routes towards the generation of metal alkylidene species with the goal of synthesizing first-row transition metal alkylidenes. To achieve this goal, pursuit of novel routes to generation masked alkylidenes was undertaken and new reactive small molecules were considered for use as alkylidene precursors.The study began with the synthesis of a library of PNP chelates of iron featuring various halide and alkyl ligands. The generation of masked alkylidene species through the utilization of a pendant amine group was unsuccessfully targeted by a variety of synthetic routes. [1.1.1]propellane was identified as a carbene precursor capable of generating stable metal alkylidene species with ruthenium, osmium, and vanadium. The reactivity of [1.1.1]propellane was investigated for a wide array of organometallic species and the scope was widened to include other propellane species, namely 1,3-dehydroadamantane. Efforts towards the synthesis of reduced titanium species with the goal of reaction with [1.1.1]propellane led to the identification of a number of interesting complexes and their reactivity was investigated in the final expansion of this work.
일반주제명  
Chemistry
일반주제명  
Inorganic chemistry
일반주제명  
Organic chemistry
키워드  
Olefin metathesis
키워드  
Propellane
키워드  
Homogenous catalysis
기타저자  
Cornell University Chemistry and Chemical Biology
기본자료저록  
Dissertations Abstracts International. 86-03B.
전자적 위치 및 접속  
로그인 후 원문을 볼 수 있습니다.

MARC

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■035    ▼a(MiAaPQ)AAI30243990
■040    ▼aMiAaPQ▼cMiAaPQ
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■1001  ▼aGeorge,  Gregory.▼0(orcid)0000-0001-5269-3214
■24510▼aSynthetic  Routes  to  Metal  Alkylidene  Complexes  that  Catalyze  Olefin  Metathesis  and  the  Utilization  of  [1.1.1]Propellane  as  a  Carbene  Precursor
■260    ▼a[Sl]▼bCornell  University▼c2024
■260  1▼aAnn  Arbor▼bProQuest  Dissertations  &  Theses▼c2024
■300    ▼a202  p
■500    ▼aSource:  Dissertations  Abstracts  International,  Volume:  86-03,  Section:  B.
■500    ▼aAdvisor:  Wolczanski,  Peter.
■5021  ▼aThesis  (Ph.D.)--Cornell  University,  2024.
■520    ▼aOlefin  metathesis  is  a  class  of  reactions  utilized  in  the  fine-chemical  and  commodities  industries.  Homogenous  catalysis  of  olefin  metathesis  can  be  performed  by  metal  alkylidene  species,  and  these  compounds  have  been  investigated  for  decades.  In  recent  years,  a  focus  has  been  placed  on  the  development  of  catalysts  using  metals  with  lower  toxicity  and  cost  when  compared  to  original  systems  utilizing  ruthenium  and  molybdenum.The  purpose  of  this  work  is  to  explore  alternative  routes  towards  the  generation  of  metal  alkylidene  species  with  the  goal  of  synthesizing  first-row  transition  metal  alkylidenes.  To  achieve  this  goal,  pursuit  of  novel  routes  to  generation  masked  alkylidenes  was  undertaken  and  new  reactive  small  molecules  were  considered  for  use  as  alkylidene  precursors.The  study  began  with  the  synthesis  of  a  library  of  PNP  chelates  of  iron  featuring  various  halide  and  alkyl  ligands.  The  generation  of  masked  alkylidene  species  through  the  utilization  of  a  pendant  amine  group  was  unsuccessfully  targeted  by  a  variety  of  synthetic  routes.  [1.1.1]propellane  was  identified  as  a  carbene  precursor  capable  of  generating  stable  metal  alkylidene  species  with  ruthenium,  osmium,  and  vanadium.  The  reactivity  of  [1.1.1]propellane  was  investigated  for  a  wide  array  of  organometallic  species  and  the  scope  was  widened  to  include  other  propellane  species,  namely  1,3-dehydroadamantane.  Efforts  towards  the  synthesis  of  reduced  titanium  species  with  the  goal  of  reaction  with  [1.1.1]propellane  led  to  the  identification  of  a  number  of  interesting  complexes  and  their  reactivity  was  investigated  in  the  final  expansion  of  this  work.
■590    ▼aSchool  code:  0058.
■650  4▼aChemistry
■650  4▼aInorganic  chemistry
■650  4▼aOrganic  chemistry
■653    ▼aOlefin  metathesis
■653    ▼aPropellane
■653    ▼aHomogenous  catalysis
■690    ▼a0485
■690    ▼a0488
■690    ▼a0490
■71020▼aCornell  University▼bChemistry  and  Chemical  Biology.
■7730  ▼tDissertations  Abstracts  International▼g86-03B.
■790    ▼a0058
■791    ▼aPh.D.
■792    ▼a2024
■793    ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17160106▼nKERIS▼z이  자료의  원문은  한국교육학술정보원에서  제공합니다.

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