Synthesis and characterization of new (N‐diphenylphosphino)‐isopropylanilines and their complexes: crystal structure of (Ph₂P S)NHC₆H₄4CH(CH₃)₂ and catalytic activity of palladium(II) complexes in the Heck and Suzuki cross‐coupling reactions

Abstract

Three new (N-diphenylphosphino)-isopropylanilines, having isopropyl substituent at the carbon 2-(1) 4-(2) or 2,6-(3) were prepared from the aminolysis of chlorodiphenylphosphine with 2-isopropylaniline, 4-isopropylaniline or 2,6-diisopropylaniline, respectively, under anaerobic conditions. Oxidation of 1,2 and 3 with aqueous hydrogen peroxide, elemental sulfur or gray selenium gave the corresponding oxides, sulfides and selenides (Ph 2 P E)NH-C 6 H 4 -2-CH(CH 3 ) 2 , (Ph 2 P E)NH-C 6 H 4 -4-CH(CH 3 ) 2 and (Ph 2 P E)NH-C 6 H 4 -2,6-{CH (CH 3 ) The complexes 1d-3d were tested and found to be highly active catalysts in the Suzuki coupling and Heck reaction, affording biphenyls and stilbenes, respectively.

Mononuclear Aluminum Complexes as Precursors for Cyanosilylation of Carbonyl Compounds

“…Solvents such as n-hexane and toluene were dried using sodium metal and LiAlH 4 under an inert atmosphere. 1 H NMR (400 MHz and 600 MHz), 13 C{ 1 H} (100 MHz and 150 MHz), 19 F{ 1 H} (376 MHz), and 31 P{ 1 H} (243 MHz) spectra were recorded on the BRUKER ADVANCE III-400 MHz and 600 MHz spectrometer. Chemical shifts (δ ppm) and coupling constants (Hz) were reported in the standard fashion for the internal standard tetramethylsilane (TMS) (δ H = 0.00 ppm).…”

“…Yield: 160 mg, 96 %. 1 H NMR (400 MHz, C 6 D 6 , 298 K): δ H 7.87 (dd, J = 13.4, 7.8 Hz, 4H, ArÀ H), 7.35 (s, 1H, ArÀ H), 7.10-7.05 (m, 2H, ArÀ H), 6.95 (dd, J = 5.8, 4.1 Hz, 6H, ArÀ H), 6.86 (dd, J = 3.8, 2.7 Hz, 3H, ArÀ H), 6.78 (s, 1H, ArÀ H), 6.66-6.61 (m, 1H, ArÀ H), 6.37 (d, J = 1.1 Hz, 1H, ArÀ H), 0.21 (s, 6H, Al (CH 3 ) 2 ). 13…”

“…Yield: 950 mg, 92 %. 1 H NMR (600 MHz, CDCl 3 , 298 K): δ H 7.67 (dt, J = 7.6, 1.3 Hz, 1H, ArÀ H), 7.64-7.59 (m, 4H, ArÀ H), 7.43-7.37 (m, 2H, ArÀ H), 7.30 (td, J = 7.7, 3.5 Hz, 4H, ArÀ H), 7.24-7.17 (m, 5H, ArÀ H), 7.16-7.12 (m, 3H, ArÀ H), 6.84 (td, J = 7.5, 1.4 Hz, 1H, ArÀ H), 6.13 (d, J = 7.1 Hz, 1H, NÀ H) ppm. 13…”

“…The design and development of novel chelate ligands continue in coordination and organometallic chemistry due to the versatile applications of their metal complexes in catalysis, medicinal chemistry, and various industrial processes. [1] Chelate ligands, characterized by their ability to coordinate with a metal ion through multiple donor atoms, typically forming a ring-like structure, play a crucial role in governing the stability, reactivity, and geometry of metal complexes. [2] Hybrid chelating ligands, which are composed of both soft and hard donor atoms, are gaining a great deal of attention due to several reasons.…”