Synthesen nitro-substituierter cis-bis(phenyl)platin(II)-verbindungen

Carbon−Heteroatom Bond-Forming Reductive Eliminations of Amines, Ethers, and Sulfides

“…It is commonly believed that decreasing electron density at the metal accelerates reductive elimination. 51 This hypothesis, which is clearly true in many cases involving variation in dative ligand electron donation, would predict that more donating aryl and amido or thiolato groups would lead to decreasing rates for reductive elimination because they would increase electron density at the metal. In contrast, theoretical work has shown that more weakly donating dative ligands, but more donating covalent ligands, accelerate reductive elimination from Pd(II) by destabilizing the metal d-orbitals on the starting metal complex.…”

C(sp2)–C(sp2) Reductive Elimination from a Diarylplatinum(II) Complex Induced by a S–S Bond Oxidative Addition at Room Temperature

“…IR in KBr (cm −1 ): 1586 s, 1487 s, 1454 s, 1397 vs, 1255 m, 1087 s, 1041 s, 1013 s, 802 vs, 754 vs, 726 s, 579 w, 543 m, 501 m. 1 H NMR (400 MHz, CD 2 Cl 2 , 273 K): δ 8.10 (d, 3 J HH = 8.1 Hz, 2H, H 7 ), 7.69 (d, 3 J HH = 8.0 Hz, 2H, H 4 ), 7.42 (pseudo t, 3 J HH = 7.6 Hz, 2H, H 6 ), 7.24 (pseudo t, 3 J HH = 7.6 Hz, 2H, H 5 ), 7.01 (d, 3 J PtH = 46.8 Hz, 3 J HH = 8.1 Hz, 4H, H o ), 6.68 (d, 3 J HH = 7.9 Hz, 4H, H m ), 2.21 (s, 6H, Me of p-MeC 6 H 4 ). 13 C{ 1 H} NMR (100 MHz, CD 2 Cl 2 , 273 K): δ 181.2 (s, C 2 ), 148.3 (s, C 8 ), 136.3 (s, 2 J PtC = 14 Hz, C o ), 134.7 (s, 4 J PtC = 8 Hz, C p ), 131.9 (s, C 9 ), 128.3 (s, 3 J PtC = 49 Hz, C m ), 127.2 (s, C 6 ), 124.5 (s, C 5 ), 121.7 (s, C 4 ), 120.3 (s, C ipso ), 117.5 (s, C 7 ), 20.5 (s, Me of p-MeC 6 H 4 ). 195 Pt{ 1 H} NMR (85 MHz, CD 2 Cl 2 , 273 K): δ −1481 (s).…”

“…The reaction mixture was stirred at room temperature for 24 h. The solvent was evaporated, and the red residue was washed with diethyl ether ( 3 J HH = 8.1 Hz, through space J HF = 5 Hz, 2 H, H 7 ), 7.70 (d, 3 J HH = 8.0 Hz, 2 H, H 4 ), 7.47 (t, 3 J HH = 7.7 Hz, 2 H, H 5 ), 7.30 (t, 3 J HH = 7.7 Hz, 2 H, H 6 ). 13 C{ 1 H} NMR (100 MHz, CD 2 Cl 2 , 298 K): δ 184.9 (s, 2 J PtC = 62 Hz, C 2 ), 150.0 (m, C 6 F 5 ), 148.8 (s, C 8 ), 147.7 (m, C 6 F 5 ), 141.6 (m, C 6 F 5 ), 137.7 (m, C 6 F 5 ), 135.2 (m, C 6 F 5 ), 122.2 (s, C 6 F 5 ), 130.5 (s, C 9 ), 125.3 (s, C 6 ), 127.8 (s, C 5 ), 121.7 (s, C 4 ), 118.5 (s, C 7 ). 19 F NMR (376 MHz, CD 2 Cl 2 , 298 K): δ −117.6 (m, 3 J FF = 26 Hz, 4 J FF = 9 Hz, 4 J FF = 6 Hz, through-space J FH = 5 Hz (from 19 F{ 1 H} experiment), 3 J FPt = 176 Hz, 2F, F o endo ), −118.9 (m, 3 J FF = 24 Hz, 4 J FF = 9 Hz, 4 J FF = 6 Hz, 3 J PtF = 176 Hz, 2F, F o exo ), −158.7 (m, 3 J F,F ≈ 25 Hz, 4 J F,F ≈ 8 Hz, 2F, F p ), −163.0 (m, 3 J F,F ≈ 24 Hz, 4 J FF = 6 Hz, 4 3 J H,H = 5.3 Hz, 4 J HH = 1.6 Hz, 5 J H,H = 0.9 Hz, 3 J HPt = 20 Hz, 2H, H 6 ), 7.43 (ddd, 3 J HH = 8.3 Hz, 3 J H,H = 7.6 Hz, 4 J HH = 1.6 Hz, 2H, H 4 ), 7.03 (d, 3 J H,Pt = 46 Hz, 3 J HH = 8.0 Hz, 4H, H o ), 6.92 (ddd, 3 J HH = 7.6, Hz, 3 J H,H = 5.3, Hz, 3 J H,H = 1.1, Hz, 2H, H 5 ), 6.89 (m, 3 J HH = 8.3 Hz, 2H, H 3 ), 6.70 (d, 3 J HH = 8.0 Hz, 4H, H m ), 2.10 (s, 6H, Me of p-MeC 6 H 4 ).…”

“…19 F NMR (376 MHz, CD 2 Cl 2 , 298 K): δ −117.6 (m, 3 J FF = 26 Hz, 4 J FF = 9 Hz, 4 J FF = 6 Hz, through-space J FH = 5 Hz (from 19 F{ 1 H} experiment), 3 J FPt = 176 Hz, 2F, F o endo ), −118.9 (m, 3 J FF = 24 Hz, 4 J FF = 9 Hz, 4 J FF = 6 Hz, 3 J PtF = 176 Hz, 2F, F o exo ), −158.7 (m, 3 J F,F ≈ 25 Hz, 4 J F,F ≈ 8 Hz, 2F, F p ), −163.0 (m, 3 J F,F ≈ 24 Hz, 4 J FF = 6 Hz, 4 3 J H,H = 5.3 Hz, 4 J HH = 1.6 Hz, 5 J H,H = 0.9 Hz, 3 J HPt = 20 Hz, 2H, H 6 ), 7.43 (ddd, 3 J HH = 8.3 Hz, 3 J H,H = 7.6 Hz, 4 J HH = 1.6 Hz, 2H, H 4 ), 7.03 (d, 3 J H,Pt = 46 Hz, 3 J HH = 8.0 Hz, 4H, H o ), 6.92 (ddd, 3 J HH = 7.6, Hz, 3 J H,H = 5.3, Hz, 3 J H,H = 1.1, Hz, 2H, H 5 ), 6.89 (m, 3 J HH = 8.3 Hz, 2H, H 3 ), 6.70 (d, 3 J HH = 8.0 Hz, 4H, H m ), 2.10 (s, 6H, Me of p-MeC 6 H 4 ). 13 C{ 1 H} NMR (100 MHz, CD 2 Cl 2 , 298 K): δ 174.9 (s, 2 J CPt = 54 Hz, C 2 ), 144.5 (s, C 6 ), 137.8 (s, C 5 ), 136.1 (s, 3 J PtC = 14 Hz, C m ), 134.0 (s, 4 J PtC = 9 Hz, C p ), 128.3 (s, 2 J PtC = 49 Hz, C o ), 126.9 (s, 4 J CPt = 34 Hz, C 3 ), 122.1 (s, 1 J PtC = 826 Hz, C ipso ), 118.5 (s, 4 X-ray Structure Determinations. The X-ray diffraction measurements were carried out on a NONIUS-kCCD area-detector diffractometer or a STOE IPDS-2/2T diffractometer with graphitemonochromated Mo Kα radiation.…”

“…In this regard, the electron deficiency at the metal center determines the reactivity of the complex in a reductive elimination reaction. − Theoretical investigations demonstrated that complexes with more electron-donating ligands participating in the bond-forming step undergo reductive elimination more quickly. , This is attributed to the fact that the bonds between the metal and the ligands with electron-withdrawing groups are stronger due to their greater ionic characters. , In addition to the electronic effects of the ligands, it is obvious that the presence of bulky ancillary ligands (the ligands that do not participate in elimination) usually accelerate the elimination process. In the study of RE reactions, the diaryl RE from arylmetal complexes ,− has a special dignity because it shows us how the electron-donating or electron-withdrawing properties of the auxiliary ligands affect the rate of the RE process.…”