60268-99-7Relevant academic research and scientific papers
Reactivity of platinum(II) triphenylphosphino complexes with nitrogen donor divergent ligands
Belli Dell’ Amico, Daniela,Bellucci, Luca,Labella, Luca,Marchetti, Fabio,Samaritani, Simona
, p. 403 - 411 (2016/10/14)
Dinuclear platinum(II) complexes [{PtCl2(PPh3)}2(μ-N–N)], where N–N is a divergent bidentate nitrogen ligand, were prepared by reacting cis-[PtCl2(PPh3)(NCMe)] with N–N in a Pt/N–N molar ratio 2. The (trans,trans)-isomers were obtained as kinetic products and recovered in good yields and high purity {1, N–N?=?pyrazine (pyrz); 2, N–N?=?4,4′-bipyridyl (bipy); 3, N–N?=?piperazine (pipz); 4, N–N?=?p-xylylendiamine (xylN2)}. Cis-[PtCl2(PPh3)(NCMe)] was also reacted with the tridentate divergent ligand 2,4,6-tris-(pyrid-4′-yl)1,3,5-triazine (py3TRIA) in molar ratio 3 with formation of the trinuclear (trans,trans,trans)-[{PtCl2(PPh3)}3(μ-py3TRIA)], 5. On the other hand, the treatment of cis-[PtCl2(PPh3)(NCMe)] with the monodentate pyridine (py) produced a mixture of both trans-[PtCl2(PPh3)(py)] (6a) and cis-[PtCl2(PPh3)(py)] (6b). The reactions of cis-[PtCl2(PPh3)(NCMe)] with N–N?=?pyrz, bipy, pipz, carried out with a Pt/N–N molar ratio 1, were monitored by31P NMR spectroscopy. Equilibria were observed in solution, involving dinuclear (trans–trans)-[{PtCl2(PPh3)}2(μ-N–N)], mononuclear [PtCl2(PPh3)(N–N)] and free N–N. The addition of an excess of the divergent ligand allowed the complete conversion to the corresponding mononuclear complexes. With the heteroaromatic ligands both geometric isomers were observed (7a, 7b and 8a, 8b, for pyrz and bipy derivatives, respectively) while with pipz the trans-isomer only was detected, 9. In the system involving bipy, the scarcely soluble dinuclear (cis,cis)-[{PtCl2(PPh3)}2(μ-bipy)], 2b, was also obtained. Products 2, 2b, 3·2(CHCl3) and 6a·0.5(C2H4?Cl2) were structurally characterized by single crystal X-ray diffraction methods.
Reactivity of geometric isomers of (-)-dichloropyridine(methyl-para-tolylsulfoxide)platinum(II) by optical rotatory dispersion
De Vekki,Spevak,Skvortsov
, p. 579 - 584 (2008/10/08)
The reactions of the optically active geometric isomers of the platinum(II) complex (-)-[Pt(Me-p-TolSO)(Py)Cl2] with several nucleophilic reagents (Py, Ph3PS, Ph3P, Ph3As, and Me2SO) were studied by optical rotatory dispersion, IR spectroscopy, and 1H and 31P NMR spectroscopy. A mechanism for the reaction is proposed.
Nucleophilic Discrimination and the trans Effect. The Kinetics of Displacement of X from trans-n- (L=Me2SO, Et2S, PMe3, PEt3, PPh3, or AsEt3; X=Cl, n=1; X=MeOH, n=0) by Neutral and Anionic Nucleophiles
Tobe, Martin L.,Treadgold, Andrew T.
, p. 2347 - 2352 (2007/10/02)
The kinetics of the reaction trans-n- + L' trans-n'- + X (X=Cl-, n=1, L=Me2SO, Et2S, PMe3, PEt3, PPh3, or AsEt3, L'=pyridine (py), Me2S, Et2S, PPh3, Me2SO, thiourea (tu), or NNN'N'-tetramethylthiourea (tmtu), n'=0; L'=Cl-, Br-, I-, or SCN-, n'=1; X=MeOH, n=0, L'=Cl-, Br-, I-, or SCN-, n'=1) have been studied in 95percent methanol and 5percent water at 25 deg C.The second-order rate constants, k2, for the anionic substrates do not follow the usual dependence upon n0Pt, the anionic nucleophiles being much less reactive than predicted.A new nucleophilicity scale, based on - as standard substrate, does give linear relationships for all the anionic substrates.The relationship between the nucleophilic discrimination and the nature of the trans ligand is discussed.
Kinetics of the reversible displacement of chloride by amines under the trans effect of phosphines, phosphites, and arsines
Gosling, Roy,Tobe, Martin L.
, p. 1235 - 1244 (2008/10/08)
The rate and equilibrium constants are reported for the reaction [Pt(L)Cl3] + am → trans-[Pt(L)(am)Cl2] + Cl (L = PMe3, PEt3, P-n-Bu3, PPh3, P(OMe)3, AsEt3; am is one of a series of amines and heterocyclic bases covering a wide range of basicity) in methanol at 30.0°C, μ = 0.50. The behavior patterns are discussed and compared with those of complexes where L is a sulfur donor ligand. The lability is strongly dependent upon the nature of the donor atom (P, As, or S) but far less sensitive to the nature of the substituents.
POLYMER-IMMOBILIZED COMPLEXES OF PLATINUM(II): THEIR PRECURSORS AND PREPARATION STUDIED BY HIGH-RESOLUTION SOLID-STATE 31P NMR USING MAGIC-ANGLE SPINNING TECHNIQUES.
Fyfe,Clark,Davies,Hayes,Wasylishen
, p. 6577 - 6584 (2007/10/02)
Solid-state **3**1P NMR employing high-power proton decoupling, cross-polarization, and magic-angle spinning has been used to characterize various polymer-immobilized phosphine ligands and their platinum complexes. The reduction of polymer (polystyrene cr
