Photochemistry of ethylene-bis(triphenylphosphine)platinum

When [(Ph₃P)₂Pt(C₂H₄)] was irradiated in several solvents and at various wavelengths, the results differ with the conditions used. In particular irradiation at 254 nm gives a new alkylplatinum(II) complex by an insertion reaction.     

Thermally induced ortho-metalation of dicarbomethoxyacetylenebis(triphenylphosphine)platinum

Heating a toluene solution of dicarhomethoxyacetylenebis(triphenylphosphine)platinum(0) at 130°C gives the ortho-metalated complex (Ph₃P)(Ph₂$\text{PC}{}_6\text{H}{}_4\text{)P}$t-trans-(COOMe)CCHCOOMe.     

Crystal structure of trans-dibromobis(triphenylphosphine)platinum(II).

Crystal structure of trans-dibromobis(triphenylphosphine)platinum(II) was determined by X-ray-crystallography. The complex crystallizes on an inversion center in distorted square planar coordination around platinum with triphenylphosphine ligands in trans positions to each other and with two molecules of dichloromethane as solvate.     

The structure of hexafluoroacetone azine bis(triphenylphosphine)platinum

The crystal structure of hexafluoroacetone azine bis(triphenylphosphine)platinum, C₄₂H₃₀F₁₂N₂P₂Pt, has been determined by single-crystal X-ray diffraction techniques. The compound crystallizes in the monoclinic space group C2/c with a 31.155(3), b 13.091(1), c 21.828(2) Å, β 109.23(1)° and Z = 8. Manual diffractometer methods (Cu radiation, λ 1.54050 Å) were used to obtain 5046 reflections with I_net ? 8 counts sec^?1 at 21°C. The structure was solved by the heavy atom method and was refined, including CH₂Cl₂ at occupancy 0.4 on a crystallographic 2-fold axis, by block-diagonal least-squares methods to R = 0.056. Location of the phenyl hydrogen atoms was not attempted. The platinum atom is σ-bonded to one CN of the azine ligand forming a $\text{PtCN}$ three-membered ring. Coordination about platinum consists of a slightly distorted square-planar arrangement of the phosphorus atoms and the bonded carbon and nitrogen atoms of the unsaturated ligand. The observed difference in PtP bond lengths is rationalized in terms of the trans-influence.     

Nitrato(triphenylphosphine) complexes of the platinum metals; Detection of triphenylphosphine oxide ligands

Reactions of some platinum group metal triphenylphosphine complexes with nitric acid afford nitrato(triphenylphosphine) derivatives in good yield; the complex “Rh(NO₃) (NO)₂(OPPh₃)₂” is positively identified as [Rh(NO₃)₂ (NO) (PPh₃)₂]     

The crystal and molecular structure oftrans-Di(methylsulphito)bis-(triphenylphosphine)platinum(II)

Summary The crystal and molecular structure oftrans-di(methylsulphito)bis(triphenylphosphine)platinum(II), Pt(SO₃Me)₂ (PPh₃)₂, derived from the reaction of Pt(PPh₃)₂ (O₂) with SO₂ in MeOH and in the presence of sodium tetraphenylborate(III), has been determined from diffractometer data. The complex crystallizes in the space group P ¯1- (C_i ¹) with one molecule in a unit cell of dimensionsa = 9.744(2) Å,b = 10.062(3) Å,c = 11.153(2) Å; = 68.59(2)°, = 82.69(2)° and = 62.25(2)°. Leastsquares refinement has led to a value of the conventional R index (on F) of 0.031 for the 3308 reflections having F²>3(F₀ ²). The complex is a typical square-planar platinum(II) complex with the platinum atom lying on a crystallographically imposed centre of symmetry. The important structural parameters are Pt-P 2.369(1) Å, Pt-S 2.308(1) Å, and the oxygen atoms complete an approximate tetrahedron about the sulphur atoms with S-O 1.448(5) Å and S-O(Me) 1.620(5) Å.     

The synthesis of a cationic ylide complex of platinum(II) by the reaction of tetrakis(triphenylphosphine)platinum(O) with choloroiodomethane.

The reaction of Pt(PPh₃)₄ with CH₂Cl1 in benzene yields the cationic ylide complex $\text{cis}$-[Pt(PPh₃)₂(CH₂PPh₃)Cl]I in high yield. This complex has been converted to $\text{cis}$-[(PPh₃)₂(CH₂PPh₃)X]X (X  Br or I) by reaction with LiBr or NaI. Reaction of $\text{cis}$-[Pt(PPH₃)I]I with iodine yields $\text{cis}$-[Pt(PPh₃)₂(CH₂PPh₃)I]I₃. Nmr data are given in support of the suggested structures.