東華大學圖書館 |

語系: 繁體中文

說明(常見問題)

回圖書館首頁

手機版館藏查詢

登入

回首頁

切換: 標籤 | MARC模式 | ISBD

Metallaboratrane Facilitated E-H Bon...

Fong, Henry.

FindBook

Google Book

Amazon

博客來

Metallaboratrane Facilitated E-H Bond Activation and Hydrogenation Catalysis.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Metallaboratrane Facilitated E-H Bond Activation and Hydrogenation Catalysis./
作者:	Fong, Henry.
出版者:	Ann Arbor : ProQuest Dissertations & Theses, : 2015,
面頁冊數:	198 p.
附註:	Source: Dissertation Abstracts International, Volume: 77-05(E), Section: B.
Contained By:	Dissertation Abstracts International77-05B(E).
標題:	Inorganic chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3739907
ISBN:	9781339317687

Metallaboratrane Facilitated E-H Bond Activation and Hydrogenation Catalysis.
Fong, Henry.

Metallaboratrane Facilitated E-H Bond Activation and Hydrogenation Catalysis. - Ann Arbor : ProQuest Dissertations & Theses, 2015 - 198 p.

Source: Dissertation Abstracts International, Volume: 77-05(E), Section: B.

Thesis (Ph.D.)--California Institute of Technology, 2015.

The E--H bond activation chemistry of tris-phosophino-iron and -cobalt metallaboratranes is discussed. The ferraboratrane complex ( TPB)Fe(N2) heterolytically activates H--H and the C--H bonds of formaldehyde and arylacetylenes across an Fe--B bond. In particular, H--H bond cleavage at (TPB)Fe(N2) is reversible and affords the iron-hydride-borohydride complex (TPB)(&mgr;--H)Fe(L)(H) (L = H2, N2). (TPB)(&mgr;--H)Fe(L)(H) and (TPB)Fe(N2) are competent olefin and arylacetylene hydrogenation catalysts. Stoichiometric studies indicate that the B--H unit is capable of acting as a hydride shuttle in the hydrogenation of olefin and arylacetylene substrates. The heterolytic cleavage of H2 by the (TPB)Fe system is distinct from the previously reported ( TPB)Co(H2) complex, where H2 coordinates as a non-classical H2 adduct based on X-ray, spectroscopic, and reactivity data. The non-classical H2 ligand in (TPB)Co(H 2) is confirmed in this work by single crystal neutron diffraction, which unequivocally shows an intact H--H bond of 0.83 A? in the solid state. The neutron structure also shows that the H2 ligand is localized at two orientations on cobalt trans to the boron. This localization in the solid state contrasts with the results from ENDOR spectroscopy that show that the H2 ligand freely rotates about the Co--H2 axis in frozen solution. Finally, the (TPB )Fe system, as well as related tris-phosphino-iron complexes that contain a different apical ligand unit (Si, PhB, C, and N) in place of the boron in (TPB)Fe, were studied for CO2 hydrogenation chemistry. The (TPB)Fe system is not catalytically competent, while the silicon, borate, carbon variants, (SiPR 3)Fe, (PhBPiPr3)Fe, and (CPiPr3)Fe, respectively, are catalysts for the hydrogenation of CO2 to formate and methylformate. The hydricity of the CO2 reactive species in the silatrane system ( SiPiPr3)Fe(N2)(H) has been experimentally estimated.

ISBN: 9781339317687Subjects--Topical Terms:

3173556
Inorganic chemistry.

Metallaboratrane Facilitated E-H Bond Activation and Hydrogenation Catalysis.
LDR:02817nmm a2200277 4500 001 2119353
005 20170619080612.5
008 180830s2015 ||||||||||||||||| ||eng d
020 $a 9781339317687
035 $a (MiAaPQ)AAI3739907
035 $a AAI3739907
040 $a MiAaPQ $c MiAaPQ
100 1 $a Fong, Henry. $3 3281222
245 1 0 $a Metallaboratrane Facilitated E-H Bond Activation and Hydrogenation Catalysis.
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2015
300 $a 198 p.
500 $a Source: Dissertation Abstracts International, Volume: 77-05(E), Section: B.
500 $a Adviser: Jonas C. Peters.
502 $a Thesis (Ph.D.)--California Institute of Technology, 2015.
520 $a The E--H bond activation chemistry of tris-phosophino-iron and -cobalt metallaboratranes is discussed. The ferraboratrane complex ( TPB)Fe(N2) heterolytically activates H--H and the C--H bonds of formaldehyde and arylacetylenes across an Fe--B bond. In particular, H--H bond cleavage at (TPB)Fe(N2) is reversible and affords the iron-hydride-borohydride complex (TPB)(&mgr;--H)Fe(L)(H) (L = H2, N2). (TPB)(&mgr;--H)Fe(L)(H) and (TPB)Fe(N2) are competent olefin and arylacetylene hydrogenation catalysts. Stoichiometric studies indicate that the B--H unit is capable of acting as a hydride shuttle in the hydrogenation of olefin and arylacetylene substrates. The heterolytic cleavage of H2 by the (TPB)Fe system is distinct from the previously reported ( TPB)Co(H2) complex, where H2 coordinates as a non-classical H2 adduct based on X-ray, spectroscopic, and reactivity data. The non-classical H2 ligand in (TPB)Co(H 2) is confirmed in this work by single crystal neutron diffraction, which unequivocally shows an intact H--H bond of 0.83 A? in the solid state. The neutron structure also shows that the H2 ligand is localized at two orientations on cobalt trans to the boron. This localization in the solid state contrasts with the results from ENDOR spectroscopy that show that the H2 ligand freely rotates about the Co--H2 axis in frozen solution. Finally, the (TPB )Fe system, as well as related tris-phosphino-iron complexes that contain a different apical ligand unit (Si, PhB, C, and N) in place of the boron in (TPB)Fe, were studied for CO2 hydrogenation chemistry. The (TPB)Fe system is not catalytically competent, while the silicon, borate, carbon variants, (SiPR 3)Fe, (PhBPiPr3)Fe, and (CPiPr3)Fe, respectively, are catalysts for the hydrogenation of CO2 to formate and methylformate. The hydricity of the CO2 reactive species in the silatrane system ( SiPiPr3)Fe(N2)(H) has been experimentally estimated.
590 $a School code: 0037.
650 4 $a Inorganic chemistry. $3 3173556
690 $a 0488
710 2 $a California Institute of Technology. $b Chemistry. $3 2096080
773 0 $t Dissertation Abstracts International $g 77-05B(E).
790 $a 0037
791 $a Ph.D.
792 $a 2015
793 $a English
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3739907