Reactions of two-coordinate phosphine platinum(0) and palladium(0) compounds. Ligand exchange and reactivities toward small molecules

Application of the New “Integrated MO + MM” (IMOMM) Method to the Organometallic Reaction Pt(PR3)2 + H2 (R = H, Me, t-Bu, and Ph)

“…22 The two-coordinate phosphine complexes PtL 2 (L ) P(c-C 6 H 11 ) 3 , P(i-Pr) 3 ) also react with H 2 at room temperature under atmospheric pressure to give the trans-PtH 2 L 2 product. 18 However, in the case of L ) P(tBu) 3 and PPh(t-Bu) 2 , the reaction practically does not take place under the same reaction conditions. The reactivity of PtL 2 toward H 2 increases in the following order: P(t-Bu) 3 < PPh-(t-Bu) 2 < P(c-C 6 H 11 ) 3 < P(i-Pr) 3 .…”

Monomeric Chini‐Type Triplatinum Clusters Featuring Dianionic and Radical‐Anionic π*‐Systems

“…[12,13] As such, af urthered understanding of the electronic structure and reactivity profiles available to these clusters continues to be of importance. Although reportedly synthesized in situ via reduction of [Pt 3 (CO) 6 ] 2 2À with Na/K alloy, it could not be crystallized or precipitated from solution, with characterization relying solely upon IR and atomic absorption spectroscopies.Interestingly,a lthough several mixed carbonyl/phosphine clusters of the type Pt 3 (m-CO) 3 (PR 3 ) 3 have been long-known, [16][17][18][19][20] their reduction to the corresponding platinates has not been reported, potentially implying that the weak p-accepting properties of triorganophosphines are insufficient to stabilize the presence of two negative charge equivalents. Although reportedly synthesized in situ via reduction of [Pt 3 (CO) 6 ] 2 2À with Na/K alloy, it could not be crystallized or precipitated from solution, with characterization relying solely upon IR and atomic absorption spectroscopies.Interestingly,a lthough several mixed carbonyl/phosphine clusters of the type Pt 3 (m-CO) 3 (PR 3 ) 3 have been long-known, [16][17][18][19][20] their reduction to the corresponding platinates has not been reported, potentially implying that the weak p-accepting properties of triorganophosphines are insufficient to stabilize the presence of two negative charge equivalents.…”

O–H Activation and Addition to Unsaturated Systems

“…6.8) [15,16]. Yoshida and Otsuka [39] reported that reaction of two coordinate platinum complexes, [PtL 2 ] (24) (a: L = P i Pr 3 , b: L = PCy 3 , c: L = PPh t Bu 2 ) with MeOH at room temperature gave stable trans-[PtH 2 L 2 ] (51), formed by β-H elimination from the corresponding oxidative addition products, hydrido(methoxo) complexes (Eq. 6.20).…”