Publisher Summary The rapid development of the chemistry of transition-metal complexes containing terminal carbene (A) or carbyne (B) ligands has been followed more recently by much research centered on bridged methylene compounds (C). As often occurs in new and developing areas of chemistry, some confusion about the nomenclature of these complexes has arisen. Protonation or alkylation of several ethynyl–metal derivatives gives the corresponding vinylidene complexes in high yield. Several vinylidene complexes of the group VI metals have been obtained by heating σ–chlorovinyl derivatives with tertiary phosphines, phosphites, arsines, or stibines. Several complexes containing μ-C=CHR ligands have been obtained directly from 1-alkynes and two equivalents (or excess) of an appropriate precurso. A general route to complexes containing propadienylidene ligands is by loss of water or alcohols from suitable carbene or vinylidene precursors, or of oxo or alkoxy functions from ynolate anions. The majority of the chemistry of vinylidene and propadienylidene complexes is concerned with their synthesis and reactions. Vinylidene is one of the best π-acceptors known and is exceeded only by SO2 and CS. The vinylidene ligand occupies an important place in the sequence of reactions linking a variety of well-known η1-carbon-bonded ligands. Metal cluster complexes containing vinylidene ligands have been considered as models of species present when olefins or alkynes are chemisorbed on metal surfaces.