23523-31-1Relevant articles and documents
Synthesis of mono- and polynuclear perhalophenyl palladium-platinum acetylide complexes. Molecular structure of (NBu4)2CPh)4>*4CH2Cl2
Espinet, Pablo,Fornies, Juan,Martinez, Francisco,Sotes, Milagros,Lalinde, Elena,et al.
, p. 253 - 267 (1991)
The reaction between CR)>n (R = tBu, Ph) and the appropriate mononuclear palladium or platinum substrate affords mononuclear derivatives of the type CR)L2> (M = Pd, Pt; R = tBu, Ph; L = PPh3, dppe).Polynuclear (NBu4)2CPh)4> (X = F, Cl; R = Ph, tBu) complexes are obtained by reaction between (NBu4)2 (X' = Cl, X = F; X' = I, X = Cl) and CR)>n (Pt:Ag ratio 1:2).Similar heterometallic derivatives Q2CR)4> (Q = PMePh3, NBu4; M = Ag, Cu; R = Ph, tBu) can be prepared by reaction of Q2CR)2> with AgCl or CuCl (Pt:M ratio 1:1).The structure of (NBu4)2CPh)4>*4CH2Cl2 has been determined by X-ray diffraction.
σ-bond metathesis between M-X and RC(O)X′ (M = Pt, Pd; X, X′ = Cl, Br, I): Facile determination of the relative Δ G values of the oxidative additions of RC(O)X to an M(0) complex, evidence by density functional theory calculations, and synthetic applications
Kuniyasu, Hitoshi,Sanagawa, Atsushi,Nakane, Daisuke,Iwasaki, Takanori,Kambe, Nobuaki,Bobuatong, Karan,Lu, Yunpeng,Ehara, Masahiro
supporting information, p. 2026 - 2032 (2013/05/09)
The novel utility of the ligand exchange reaction between M-X and RC(O)X′ (X, X′ = halogen; R = aryl, alkyl) is described. The relative ΔGs (ΔΔGs) of the oxidative additions of acid halides RC(O)X to M(PPh3)2Ln (M = Pt, Pd) were determined using the halogen-exchange reactions between X of trans-M(X)[C(O)R](PPh3)2 and X′ of RC(O)X′. Experimental thermodynamics data are reasonably consistent with those obtained by density functional theory (DFT) calculations. Activation parameters obtained by experiments as well as a systematic DFT study supported the fact that reactions occurred through slightly distorted quadrangular pentacoordinated σ-bond metatheses, in which the Cl atom underwent a more indirect course than the Br atom. Moreover, exchange reactions were employed as the accessible prototype for the conversion of halogen ligands of nickel triad complexes into heavier halogen ligands.
Cooperation between cis and trans influences in cis-Pt II(PPh3)2 complexes: Structural, spectroscopic, and computational studies
Rigamonti, Luca,Forni, Alessandra,Manassero, Mario,Manassero, Carlo,Pasini, Alessandro
, p. 123 - 135 (2010/03/04)
The relevance of cis and trans influences of some anionic ligands X and Y in cis-[PtX2(PPh3)2] and cis-[PtXY(PPh 3)2] complexes have been studied by the X-ray crystal structures of several derivatives (X2 = (AcO)2 (3), (NO3)2 (5), Br2 (7), I2 (11); and XY = Cl(AcO) (2), Cl(NO3) (4), and Cl(NO2) (13)), density functional theory (DFT) calculations, and one bond Pt-P coupling constants, JPtp. The latter have allowed an evaluation of the relative magnitude of both influences. It is concluded that such influences act in a cooperative way and that the cis influence is not irrelevant when rationalizing the 1 JPtp values, as well as the experimental Pt-P bond distances. On the contrary, in the optimized geometries, evaluated through B3LYP/def2-SVP calculations, the cis influence was not observed, except for compounds CIPh (21), Ph2 (22), and, to a lesser extent, Cl(NO2) (13) and (NO2) 2(14). A natural bond order analysis on the optimized structures, however, has shown how the cis influence can be related to the s-character of the Pt hybrid orbital involved in the Pt-P bonds and the net atomic charge on Pt. We have also found that in the X-ray structures of cis-[PtX 2(PPh3)2] complexes the two Pt-X and the two Pt-P bond lengths are different each other and are related to the conformation of the phosphine groups, rather than to the crystal packing, since this feature is observed also in the optimized geometries.
