324765-07-3Relevant academic research and scientific papers
Ligand discrimination in the reaction of nitrones with [PtCl2(PhCN)2]. Selective formation of mono-oxadiazoline and mixed bis-oxadiazoline complexes under thermal and microwave conditions
Desai, Bimbisar,Danks, Timothy N.,Wagner, Gabriele
, p. 166 - 171 (2007/10/03)
[2+3] Cycloaddition of nitrones to the nitrile ligands in the complexes cis- or trans-[PtCl2(PhCN)2] occurs under ligand differentiation and allows for selective synthesis of complexes of the type cis- or trans-[PtCl2(oxadiazoline)-(PhCN)]. Microwave irradiation enhances the reaction rates of the cycloaddition considerably and further favours the selectivity towards the mono-cycloadduct with respect to thermal conditions, because the first cycloaddition is accelerated to a higher extent than the second one. Reaction of the trans-substituted mono-oxadiazoline complexes with a nitrone different from the one used for the first cycloaddition step gives access to mixed bis-oxadiazoline compounds of the composition trans-[PtCl2(oxadiazoline-a)(oxadiazoline-b)]. The corresponding cis-configured complexes, however, do not undergo further cycloaddition. All reactions described occur without isomerisation of the stereochemistry around the platinum center, independently of whether thermal or microwave heating is applied.
Zirconium complexes of fluorinated aryl diamides
O'Connor, Paul E.,Morrison, Darryl J.,Steeves, Sheryl,Burrage, Katherine,Berg, David J.
, p. 1153 - 1160 (2008/10/08)
The reaction of excess ArFNHLi with (ICH2CH2OCH2)2 affords the new diamines (ArF CH2CH2OCH2)2 (1, ArF = C6F5; 2,
[2 + 3] Cycloaddition of nitrones to platinum-bound organonitriles: Effect of metal oxidation state and of nitrile substituent
Wagner,Haukka,Frausto da Silva,Pombeiro,Kukushkin
, p. 264 - 271 (2008/10/08)
The ligated benzonitriles in the platinum(II) complex [PtCl2(PhCN)2] undergo metal-mediated [2 + 3] cycloaddition with nitrones -ON+(R3)=C(R1)(R2) [R1/R2/R3 = H/Ph/Me, H/p-MeC6H4/Me, H/Ph/CH2Ph] to give Δ4-1,2,4-oxadiazoline complexes, [PtCl2{N=C(Ph)O-N(R3)-C(R1)(R2)} 2] (2a, 4a, 6a), as a 1:1 mixture of two diastereoisomers, in 60-75% yields, while [PtCl2(MeCN)2] is inactive toward the addition. However, a strong activation of acetonitrile was reached by application of the platinum(IV) complex [PtCl4(MeCN)2] and both [PtCl4-(RCN)2] (R = Me, Ph) react smoothly with various nitrones to give [PtCl4{N=C(R)O-N(R3)-C(R1)(R2)} 2] (1b-6b). The latter were reduced to the corresponding platinum(II) complexes [PtCl2{N=C(R)O-N(R3)-C-(R1)(R2)} 2] (1a-6a) by treatment with PhCH2NHOH, while the reverse reaction, i.e. conversion of 1a-6a to 1b-6b, was achieved by chlorination with Cl2. The diastereoisomers of [PtCl2{N=C(R)O-N(R3)-C(R1)(R2)} 2] (1a-6a) exhibit different kinetic labilities, and liberation of the Δ4-1,2,4-oxadiazolines by substitution with 1,2-bis(diphenylphosphino)ethane (dppe) in CDCl3 proceeds at different reaction rates to give free N=C(R)O-N(R3)-C(R1)(R2) and [PtCl2(dppe)] in almost quantitative NMR yield. All prepared compounds were characterized by elemental analyses, FAB mass spectrometry, and IR and 1H, 13C{1H}, and 195Pt (metal complexes) NMR spectroscopies; X-ray structure determination of the first (Δ4-1,2,4-oxadiazoline)Pt(II) complexes was performed for (S,S)/(R,R)-rac-[PtCl2{N=C(Me)O-N(Me)-C(H)Ph}2] (1a) (a = 9.3562(4), b = 9.8046(3), c = 13.1146(5) A; α = 76.155(2), β = 83.421(2), γ = 73.285(2)°; V = 1117.39(7) A3; triclinic, P1, Z = 2), (R,S)-meso-[PtCl2-(N=(Ph)O-N(Me)-C(H)Ph)2] (2a) (a = 8.9689(9), b = 9.1365(5), c = 10.1846(10) A; α = 64.328(6), β = 72.532(4), γ = 67.744(6)°; V = 686.82(11) A3; triclinic, P1, Z = 1), (S,S)/(R,R)-rac-[PtCl2(N=C(Me)O-N(Me)-C(H)(p-C6H 4Me))2] (3a) (a = 11.6378(2), b = 19.0767(7), c = 11.5782(4) A; β = 111.062(2)°; V = 2398.76(13) A3; monoclinic, P21/c, Z = 4), and (S,S)/(R,R)-rac-[PtCl2(N=C(Me)O-N(CH2Ph)-C(H)Ph 2] (5a) (a = 10.664(2), b = 10.879(2), c = 14.388(3) A; α = 73.11(3), β = 78.30(3), γ = 88.88(3)°; V = 1562.6(6) A3; triclinic, P1, Z = 2).
