Zur Reaktivität von π‐(η 5 ‐)‐Cyclopentadienyl‐palladium‐σ‐(η 1 ‐)‐allyl‐ und π‐(η 5 ‐)‐Cyclopentadienyl‐palladium‐halogenid‐Komplexen; neue ortho ‐Metallierungsreaktionen von Tri‐ o ‐tolylphosphit ,

One the Reactivity of π‐(η 5 ‐)‐Cyclopentadienylpalladium‐δ‐(η 1 ‐)‐allyl‐ and π‐(η 5 ‐)‐Cyclopentadienylpalladiumhalide Complexes; New ortho ‐Metallation Reactions of Trio‐o‐tolylphosphit Teil des Hauptvortrages von H. W. an der Jahrestagung der Chemical Society, York (U.K.), 7.‐11.4.1975.20.Mitt. der Reihe «Untersuchungen zur Reaktivität von Metall‐π‐Komplexen»; 19.Mitteilung siehe [1]. (η 5 ‐C 5 H 5 )Pd(η 3 ‐2‐ClC 3 H 4 ) reacts with Lewis bases L[PPh 3 , P(OPh) 3 , P(O‐ p ‐Tol) 3 , P(O‐ o ‐Tol) 3 , CO] in a 1:1 molar ratio to give the η 1 ‐2‐chloroallyl complexes 2a – 2e . (η 5 ‐C 5 H 5 )‐Pd(η 1 ‐2‐ClC 3 H 4 )P(O‐ o ‐Tol) 3 ( 2d ) which is stable at room temperature has been isolated as a red oil. It represents the first well‐characterized η 1 ‐allylpalladium derivative. 2a – 2d eliminate allene to form (η 5 ‐C 5 H 5 )PdClL ( 5a – 5d ). The tri‐ o ‐tolylphosphite complex 5d reacts with NaI to give (η 5 ‐C 5 H 5 )PdIP(O‐ o ‐Tol) 3 ( 6 ) and on Al 2 O 3 to give (η 5 ‐C 5 H 5 )Pd[P(OC 6 H 3 ‐ o ‐Me)(OC 6 H 4 ‐ o ‐Me) 2 ] ( 7 ). Elimination of HCl leading to ortho ‐metallation of one of the six‐membered rings of tri‐ o ‐tolylphosphite also occurs in the reaction of PdCl 4 2− and P(O‐ o ‐Tol) 3 to form Pd 2 Cl 2 [P(OC 6 H 3 ‐ o ‐Me)(OC 6 H 4 ‐ o ‐Me) 2 ] 2 ( 9 ). This reacts with TlC 5 H 5 to give 7 . The preparation of Pd 2 Cl 4 [P(O‐ o ‐Tol) 3 ] 2 ( 8 ) and Pd 2 I 2 [P(OC 6 H 3 ‐ o ‐Me)(OC 6 H 4 ‐ o ‐Me) 2 ] 2 ( 10 ) is also reported.