Über Reaktionen organischer Radikale mit Palladium- und Platinkomplexen / Reactions of Organic Radicals with Palladium and Platinum Complexes

2,4,6-Trinitrophenylgold(I) complexes. X-Ray crystal structures of [Au(SbPh3)4][Au{C6H2(NO2)3-2,4,6}2]·Et2O and [Au{C6H2(NO2)3-2,4,6}(dmphen)](dmphen = 2,9-dimethyl-1,10-phenanthroline)

“…the ligand dmphen appearing as an AB system (centred at 6 7.94) corresponding to protons bonded to carbon atoms C (22), C (23), C(32), and C(33) (see Figure 2) and two singlets due to protons bonded to C(26) and C(36) (6 7.77) and to methyl groups (6 2.99). The co-ordination geometry of complex (4) (Figure 2) can be described as intermediate between two-and three-co-ordination; such geometry can be regarded as a compromise between the marked tendency of gold (1) to two-co-ordination and the presence of a rigid bidentate ligand. 16 The Au-N bond lengths are 2.136(3) 8, to N(4) and 2.573(3) A to N(5).…”

“…The reaction of [ PPh,( CH,Ph)] [AuCI,] in refluxing acetone with [ Hg{C,H,( N0,),-2,4,6},] (1 : 0.55) and excess of NMe,CI affords NMeJHgCI,] and [PPh,(CH,Ph)] [Au{C,H,( NO,),- 2,4,6}Cl] (1 ). Complex (1) reacts with excess of both NaCI0,-H,O and tetrahydrothiophene (tht) at room temperature to give [Au{C,H,( N02),-2,4,6}(tht)] ( 2) which reacts with SbPh, (1 : 2) or with excess of 2,9-dimethyl-1 ,I O-phenanthroline (dmphen) to give [Au(SbPh,),] [Au{C,H,( NO,),- 2,4,6},] (3) or [Au{C,H,( No2),-2,4,6}(dmphen)] (4), respectively. Crystal structures were determined for complexes (3) and (4).…”

“…However, the ips0 C-C-C angles [ 108.9( 1 l), 1 13.4( 13)O] are much smaller than ideal sp2 values, which is consistent with the observation of a mean ips0 c-c-c angle of 114.7' in AU-C~FS complexes '' and also with the value of 112.9(3)' found2 in cis-[PdC12(C6H2-(N02),-2,4,6) (S(O)Me,)] -. The electron-withdrawing groups concentrate p character in the ring bonds and thus more s character in the Au-C bonds.The co-ordination geometry of complex (4) (Figure2) can be described as intermediate between two-and three-co-ordination; such geometry can be regarded as a compromise between the marked tendency of gold(1) to two-co-ordination and the presence of a rigid bidentate ligand.16 The Au-N bond lengths…”

Attempts To Prepare Palladium(II) Complexes with the O,C,O Pincer Aryl Ligand C6(NO2)2-2,6-(OMe)3-3,4,5

“…This is the method most frequently employed in the preparation of nitroaryl complexes. Other methods using organolithium or tin derivatives, oxidative-addition reactions, − arylhydrazonium salts, or direct metalation of arenes − have more limited applicability. Recently, even the nitration of aryl complexes has been reported. , Our interest in the synthesis of nitroaryl complexes is based on the great stability of these complexes (allowing, for example, the synthesis of carbonyl arylpalladium(II) complexes 70 ) and on the study of the structural properties and the coordination ability of the nitro group.…”

“…This is the method most frequently employed in the preparation of nitroaryl complexes. Other methods using organolithium or tin derivatives, 77 oxidative-addition reactions, [78][79][80] arylhydrazonium salts, 81 or direct metalation of arenes [82][83][84] have more limited applicability. Recently, even the nitration of aryl complexes has been reported.…”