Reactions of d(0) tungsten alkylidyne complexes with O2 or H2O. Formation of an oxo siloxy complex through unusual silyl migrations.
نویسندگان
چکیده
(Me3SiCH2)3(Me3SiC≡)W←O=PMe3 (1), an adduct between (Me3SiCH2)3W≡CSiMe3 (2) and O=PMe3, reacts with O2 to give O=W(OSiMe3)(CH2SiMe3)3 (3) and CO2. Reaction of 2 with H2O yields 3 and the trimer [(μ-O)W(CH2SiMe3)2(=O)(THF)]3 (4). In the reaction of D2O with 2, 3-d(n) and methane isotopologues CH2D2, CHD3 and CD4 have been observed.
منابع مشابه
Reactions of zirconium amide amidinates with dioxygen. Observation of an unusual peroxo intermediate in the formation of oxo compounds.
Reaction of d(0) Zr(NMe2)2[MeC(N(i)Pr)2]2 (1) with O2 at -30 °C gives three Zr containing products: a peroxo trimer {(μ-η(2):η(2)-O2)Zr[MeC(N(i)Pr)2]2}3 (2), an oxo dimer {(μ-O)Zr[MeC(N(i)Pr)2]2}2 (3), and an oxo polymer {(μ-O)Zr[MeC(N(i)Pr)2]2}n (4). is a rarely observed peroxo complex from the reaction of a d(0) complex with O2.
متن کاملAlkyne metathesis by molybdenum and tungsten alkylidyne complexes.
Alkyne metathesis by molybdenum and tungsten alkylidyne complexes is now ~45 years old. Progress in the practical aspects of alkyne metathesis reactions with well-defined complexes, as well as applications, in the last decade, guarantees that it is destined to become a useful method for the synthesis of organic molecules.
متن کاملRecent advances in the development of alkyne metathesis catalysts
The number of well-defined molybdenum and tungsten alkylidyne complexes that are able to catalyze alkyne metathesis reactions efficiently has been significantly expanded in recent years.The latest developments in this field featuring highly active imidazolin-2-iminato- and silanolate-alkylidyne complexes are outlined in this review.
متن کاملDissymmetric dinuclear transition metal complexes as dual site catalysts for the polymerization of ethylene
A series of dissymmetric dinuclear complexes were synthesized, as dual site catalysts in ethylene polymerization, by coupling the allylated a-diimine complexes of the metals Ti, Zr, V, Ni and Pd with the ansa-zirconocene complex [C5H4-SiH(Me)-C5H4]ZrCl2 possessing a hydride silane moiety. The different stages of syntheses included the formation of bis(cyclopentadienide)methyl silane which was u...
متن کاملCarbon dioxide cleavage across a tungsten-alkylidyne bearing a trianionic pincer-type ligand.
The cleavage of carbon dioxide by the tungsten alkylidyne [CF3-ONO]W[triple bond, length as m-dash]CCtBu(THF)2 (1) {where CF3-ONO = (MeC6H3[C-(CF3)2O])2N3-}, is reported. Splitting of CO2 yields the tungsten oxo ketene complex [CF3-ONO]W(O){(CH3)3CC[double bond, length as m-dash]C[double bond, length as m-dash]O} (6). The proposed pathway occurs through initial cycloaddition of W[triple bond, l...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Chemical communications
دوره 49 83 شماره
صفحات -
تاریخ انتشار 2013