Structural and electronic features of triphenylstibine-functionalized Fischer carbene complexes of molybdenum(0)

Abstract

Highlights  X-ray structure of novel triphenylstibine containing Mo(0) Fischer carbene complexes  X-ray photoelectron spectroscopy binding energies of Mo 3d 5/2 photoelectron lines  X-ray photoelectron spectroscopy binding energies of Sb 2p3/2 photoelectron lines  QTAIM bonding paths stabilize preferred orientation of aryl carbene substituent  Interactions between donor and empty acceptor NBOs stabilize aryl group orientation

Ag(I)-Catalyzed Tandem Reaction of Conjugated Ene-yne-ketones in the Presence of PhI(OAc)2 and Triethylamine: Synthesis of 2-Alkenylfurans

“…On the basis of these investigations and reports in the literature, − a plausible mechanism to rationalize this cyclization–olefination (Scheme ) is depicted in Scheme . First, the acetylenic carbon–carbon triple bond is activated by the coordination of enynone 1 with the Ag­(I) ion .…”

“…In particular, transition-metal-catalyzed cascade reactions of conjugated ene-yne-ketones have provided useful approaches for the synthesis of furan derivatives. Among them, Pd­(II), Cu­(I), , Cu­(II), zinc, Au­(III or I), Rh­(II or I), and Cr(0), W(0), Ru­(II), Rh­(I), Pt­(II) species-intermediated syntheses of furan derivatives have attracted great attention. These cascade reactions proceed via 5- exo -dig cyclization involving a nucleophilic attack of carbonyl oxygen at a transition-metal-activated triple bond, which can also be represented as a Zwitterionic intermediate, to produce a relatively stable (2-furyl)­carbene–metal complex .…”

Developments in the chemistry of stibine and bismuthine complexes

“…The kinetics of substitution of pyridine or piperidine (L) in [M(CO)4(L)(SbPh3)] (M = Mo, W) by phosphines and phosphites have been determined[44]. Various Fischer carbene (L') complexes of types [Mo(CO)4(SbPh3)(L')][45,46] and [W(CO)4(SbPh3)(L')][47] have been synthesised and their structures and electrochemical properties explored.…”

Mo Fischer Carbene Complexes: A DFT Study on the Prediction of Redox Potentials

“…9 Substitution of one or more carbonyl ligands on the carbene complex by ligands such as phosphines conveyed additional air stability to the complexes. [10][11][12] Several arene-and heteroarene Mo Fischer carbene complexes have been structurally characterized, containing phenyl, [12][13][14] thiophene derivatives, [15][16][17] furan, 16,[18][19][20] Nmethyl pyrrole 15 or ferrocenyl 21,22 as carbene substituents. From the structural data, it is clear that variations in the metal environment and carbene substituent affect the electronic properties of the complexes.…”