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Beilstein J. Org. Chem. 2012, 8, 1554–1563, doi:10.3762/bjoc.8.177
Graphical Abstract
Scheme 1: Heterolytic cleavage of H2 by a phosphine/borane FLP by H2 polarization in the P–B cavity [5,11].
Scheme 2: Insertion of carbon dioxide into a phosphine/borane FLP [14].
Figure 1: Simplified frontier-molecular-orbital diagrams for (a) Mδ+═Eδ− and (b) Mδ−═Eδ+ FLPs (n = 1 for line...
Figure 2: Quenching of M═E FLPs by dimerization: (a) generic Mδ+═Eδ− case, and (b) Bergman's arylimido zircon...
Scheme 3: Oxygen-atom extrusion from CO2 by a Ta(V) neopentylidene [27].
Scheme 4: Oxygen-atom transfer from acetone at a Zr(IV) imide [28].
Scheme 5: Alkyne cycloaddition at a Zr(IV) imide [38].
Scheme 6: Nitrile-alkyne cross metathesis at a W(VI) nitride [40,41].
Scheme 7: C–H and H–H addition across a zirconium(IV) imide [42].
Scheme 8: Formal [2 + 2] cycloaddition of methyl isocyanate at a ruthenium silylene [58].
Scheme 9: Oxygen-atom transfer from phenyl isocyanate to a cationic terminal borylene [60].
Scheme 10: Coupling of a phosphorus ylide with an iridium methylene [62].
Scheme 11: Reactions of (PNP)Ir═C(H)Ot-Bu with oxygen-containing heterocumulenes [71].
Scheme 12: Reductive coupling of two CS2 units at (PNP)Ir═C(H)Ot-Bu [73].
Figure 3: Single-crystal X-ray structure of a silver(I) triflate adduct of (PNP)Ir═C(H)Ot-Bu with most H atom...
Scheme 13: Possible routes to C–H functionalization by 1,2-addition across a polarized metal–element multiple ...
Scheme 14: Alkoxycarbene formation by double C–H activation at (PNP)Ir [88].
Scheme 15: Catalytic oxidation of MTBE by multiple C–H activations and nitrene-group transfer to a Mδ−═Eδ+ FLP ...