Progress in Inorganic Chemistry, Volume 27 by Stephen J. Lippard

By Stephen J. Lippard

This finished sequence of volumes on inorganic chemistry presents inorganic chemists with a discussion board for severe, authoritative reviews of advances in each zone of the self-discipline. each quantity studies contemporary growth with an important, up to date choice of papers by way of the world over well-known researchers, complemented through distinctive discussions and entire documentation. every one quantity contains a entire topic index and the sequence encompasses a cumulative index in addition.

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A). D. Miscellaneous Fischer has very recently noted that siloxycarbenecomplexes behave quite differently from their alkoxy counterparts in the presence of nucleophilic agents REACTIONS OF TRANSITION METAL CARBENE COMPLEXES 37 (21 I ) . Although the silicon-containing complexes react like the alkoxy compounds in several other ways, it appears to be very difficult to cause nucleophilic displacement of the alkylsiloxy group from the Ccarb atom. (co)5w=c (103) \C&Me M = Li;R = Ph M = Na; R = PhO, M e 0 Apparently ( d - p ) ~exchange between silicon and oxygen allows a greater electron donation from oxygen to the Ccirb, thereby strengthening this bond relative to the case in alkoxycarbenes.

In dioxane, REACTlONS OF TRANSITION METAL CARBENE COMPLEXES ,OMe (C0)5Cr=C 34 \Rf HX RNHJY - . (CO),Cr-C 31 - ‘R’ 36 H-X H-X dMe - I 37 - 38 (CO),Cr=C 35 H /NR ‘R + MeOH + HX + Y Scheme 2. Mechanism for the aminolysis of carbene complexes. however, the rate is only second order in amine since the polar solvent molecules can function as proton acceptors. The negative Arrhenius activation energy exhibited by the aminolysis reaction is a direct consequence of the important catalyzing influence of the synchrqnous presence of two hydrogen bonds.

Fischer has now succeeded in isolating the tetrahedral intermediate, 46, and has obtained similar results upon warming it (152). An analogous homolytic cleavage of the,carbene ligand was observed when an alkoxycarbene complex was treated with iodocyanide (198). FREDERICK J. BROWN 36 2(cO),Cr=C - ,OMe OMe Ph 1 1 ICN P 'h (99) OMe Ph Casey has taken advantage of the polarization of the metal-C,,,b bond in arylmethoxycarbene complexes by reacting them with Wittig reagents (48). The expected nucleophilic attack on the electropositive Ccarb occurs to form a betaine-like intermediate, 47, which subsequently fragments to an enol ether.

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