Platinum carbonyls and their use in homogeneous catalysis

Reactivity of [trans-PtH(C⋮CC5H4N-2)(PPh3)2] toward [cis-Pt(C6F5)2(thf)2]. Synthesis of an Unusual Triplatinum Cluster-Substituted Platinum Complex

“…On the other hand, if we assume that the alkynyl group donates four electrons to the central cationic [Pt 3 ] + core and the μ 3 -κ C α :η 2 α , β :κ N -CHCHC 6 H 5 N-2 is treated as a five-electron donor, then the platinum atoms are in formal oxidation states (II, I, I), and the valence electron count for this fragment cluster is 44 e - . A large number of planar platinum triangle neutral (with 42 or 44 valence electron count), anionic, or cationic (44 valence electron count) clusters are presently known, , but complex 3 is unique, not only due to its unprecedented formation but also in that it displays very unusual ligands. In particular, the presence of the face-capping vinyl and edge-bridging metallaalkynyl structures is novel.…”

Coordinatively unsaturated clusters: the rapid reversible addition of two carbonyl ligands to a trinuclear platinum cluster

“…The VSTT of precursor 3d was carried out at 350 °C for 3 h to increase the percent decomposition of starting material (85% decomposition at 300 °C). In this condition compound 3d was completely pyrolyzed to give quantitatively the heterocyclic compound 2,2-dimethyl-3-(trimethylsilyl)-2-siloxazolidine (5d).n Interestingly we have not observed cyclodisilazane (6) which was expected as a silanimine dimer product as shown in Scheme I. This result indicates that the 1,5-elimination of trimethylmethoxysilane is favored over the 1,2-elimination12 under this condition.…”

Reorientation of the alkyne moiety in Fe3(CO)9(RC.tplbond.CR) clusters induced by a two-electron electrochemical reduction

“…The proposed assignment is similar to that of Fe3(CO)9(EtC2Et) previously discussed. 5 The resonances assigned to C' atoms and their R' substituents show a marked downfield shift probably due to the paramagnetic deshielding effect of the non-bonding electrons of all the three iron atoms. From the reaction of methylphenylacetylene a product, apparently pure, is obtained from TLC separation and subsequent n-heptane crystallization.…”

“…were employed in the above-mentioned experimental conditions, but no products of formula Fe3(CO)9(RC2R) could be achieved: the main products being always the "ferróle" derivatives Fe2(CO)6(alkyne)2, along with the butatriene complex Fe2(CO)e(MeC====C=C====CH2) for the diol ligand only.12 Thus the µ3-/2-± bonding mode seems to be thermodynamically stable only for unfunzionalized aliphatic or aromatic substituents, which do not strongly perturb the delicate alkyne-cluster charge balance. 5,6 In Table I the and 13C NMR data of the Fe3(CO)9(RC2R) series are summarized. The proposed assignment is similar to that of Fe3(CO)9(EtC2Et) previously discussed.…”