342891-52-5Relevant academic research and scientific papers
Chemical transformations of cis-W(CO)4(C5H 5N)2 in the ring-opening metathesis polymerization of norbornene
Bencze,Biro,Szabo-Ravasz,Mihichuk
, p. 499 - 503 (2004)
The six-coordinate W0 complex cis-W(CO)4(C 5H5N)2 has been found to be active in the in situ formation of a carbene species from norbornene, which generates a typical ring-opening metathesis product (ROMP). A proposed mechanism of initiation suggests that the reaction involves a 2,3-hydrogen shift in the coordinated norbornene (η2 → η1). The initiating carbenoid group is identified from the products of the spontaneous carbene-CO coupling and Wittig reactions test. Formation of W(CO)3(η 6-C6H5CH3) when toluene is the solvent, followed by reaction with the carbene, is blamed for catalyst deactivation.
Radical Reactions of Bicycloheptan-3-spiro-2'-oxiranes
Bowman, W. Russell,Brown, David S.,Burns, Catherine A.,Marples, Brian A.,Zaidi, Naveed A.
, p. 6883 - 6896 (2007/10/02)
Tributyltin hydride reduction of 2-bromo- and 2-keto-bicycloheptan-3-spiro-2'-oxiranes gives ring opening of the oxirane-ringes via intermediate 3-(spiro-2'-oxiranyl)bicycloheptan-2-yl radicals, whereas reduction of the analogous 2-(thiocarbonyl)imidazolides) unusually yields the 2-methoxy derivatives and does not proceed by the expected normal fragmentation to yield 3-(spiro-2'-oxiranyl)bicycloheptan-2-yl radicals and subsequent ring-opening of the oxirane rings.
Reactions of Benzyl Carbinols with Fluorosulfuric Acid
Barrow, Colin J.,Bright, Steven T.,Coxon, James M.,Steel, Peter J.
, p. 2542 - 2549 (2007/10/02)
A series of benzyl carbinols have been reacted with HSO3F at -78 deg C, the solutions quenched, and the products isolated and identified.A variety of reaction modes occur including reduction (3-methyl- and 4-methyl-1-benzylcyclohexanol), rearrangement and
Mechanism of Initiation of the Metathesis of Norbornene using W(CO)3Cl2(AsPh3)2 as Catalyst
Bencze, Lajos,Kraut-Vass, Anna,Prokai, Laszlo
, p. 911 - 912 (2007/10/02)
Low molecular-weight derivatives obtained during ring-opening polymerisation of norbornene using W(CO)3Cl2(AsPh3)2 as catalyst indicate that a 2,3-hydrogen shift is a key step for the formation of the carbene initiator.
