A series of planar-chiral ferrocene alkenylphosphines, (S-p)-2-(diphenylphosphino)-1-vinylferrocene (2), (S-p)-2-(diphenylphosphino)-1-(prop-1-en-1-yl)ferrocene (3; as a mixture of Z and E isomers in ca. 5:1 ratio), and (E,S-p)-2-(diphenylphosphino)-1-(2-phenylethen-1-yl)ferrocene ((E)-4), was obtained by Wittig and Horner-Wadsworth Emmons reactions from the common precursor, (S-p)-2-(diphenylphosphino) ferrocene-1-carboxaldehyde (1). Coordination properties of these novel ferrocene donors were studied in their palladium(II) and tungsten(0)-carbonyl complexes. The reaction between 2 and [{Pd(mu-Cl)(L-NC)} (2)] (5, L-NC = 2-{(dimethylamino)methyl-kappa N}phenyl-kappa C-1) gave the bridge-cleavage product [PdCl(L-NC)(2-kappa P)] (6) while the reaction with [Pd(L-NC)(MeCN)(2)]ClO4 (7) yielded the cationic bis(chelate) [Pd(L-NC)(2-n(2:)kappa P)]ClO4 (8). Chelate complexes of the type [W(CO)(4)(L-n(2):kappa P)] (9 with L = 2; (Z/E)-10 with L = (Z/ E)-3) were obtained by reacting [W(CO)(4)(cod)] (cod) n(2): n(2)-cycloocta-1,5-diene) with the appropriate phosphinoalkene in refluxing toluene while a similar reaction with (E)-4 yielded mixtures of [W(CO)(5-)(4-kappa P)] ((E)-11) and [W(CO)(4)(4-n(2):kappa P)] ((E)-12). All compounds were characterized by spectral methods (multinuclear NMR, IR, MS, and CD), and the structures of 1, 2, 8, 9, (Z/E)-10, and (E)-11 were corroborated by X-ray diffraction analysis. Ligands 2 and (E)-4 as well as their complexes 6, 8, 9, (E)-11, and (E)-12 were further studied by electrochemical methods.