53103-03-0Relevant academic research and scientific papers
Iron-Catalyzed Ortho C-H Methylation of Aromatics Bearing a Simple Carbonyl Group with Methylaluminum and Tridentate Phosphine Ligand
Shang, Rui,Ilies, Laurean,Nakamura, Eiichi
, p. 10132 - 10135 (2016)
Iron-catalyzed C-H functionalization of aromatics has attracted widespread attention from chemists in recent years, while the requirement of an elaborate directing group on the substrate has so far hampered the use of simple aromatic carbonyl compounds such as benzoic acid and ketones, much reducing its synthetic utility. We describe here a combination of a mildly reactive methylaluminum reagent and a new tridentate phosphine ligand for metal catalysis, 4-(bis(2-(diphenylphosphanyl)phenyl)phosphanyl)-N,N-dimethylaniline (Me2N-TP), that allows us to convert an ortho C-H bond to a C-CH3 bond in aromatics and heteroaromatics bearing simple carbonyl groups under mild oxidative conditions. The reaction is powerful enough to methylate all four ortho C-H bonds in benzophenone. The reaction tolerates a variety of functional groups, such as boronic ester, halide, sulfide, heterocycles, and enolizable ketones.
Photo- and Thermal Isomerization of (TP)Fe(CO)Cl2 [TP = Bis(2-diphenylphosphinophenyl)phenylphosphine]
Li, Ping,De Bruin, Bas,Reek, Joost N. H.,Dzik, Wojciech I.
, p. 5009 - 5014 (2015)
The title complex displayed structural flexibility via photo- and thermal-isomerization reactions between three isomers: (mer-TP)Fe(CO)Cl2 (A), unsym-(fac-TP)Fe(CO)Cl2 (B), and sym-(fac-TP)Fe(CO)Cl2 (C). Irradiation of A a
Luminescent Triphosphine Cyanide d10 Metal Complexes
Chakkaradhari, Gomathy,Chen, Yi-Ting,Karttunen, Antti J.,Dau, Minh Thuy,J?nis, Janne,Tunik, Sergey P.,Chou, Pi-Tai,Ho, Mei-Lin,Koshevoy, Igor O.
, p. 2174 - 2184 (2016)
Coinage metal cyanides efficiently react with a triphosphine. PPh2C6H4-PPh-C6H4PPh2 (P3). to give the complexes M(P3)CN, where M = Cu (1), Ag (2), and Au (3), which ca
Alkynyl triphosphine copper complexes: Synthesis and photophysical studies
Chakkaradhari, Gomathy,Belyaev, Andrey A.,Karttunen, Antti J.,Sivchik, Vasily,Tunik, Sergey P.,Koshevoy, Igor O.
, p. 13294 - 13304 (2015)
A rigid triphosphine PPh2C6H4–PPh–C6H4PPh2 (P3) reacted with Cu+ and a stoichiometric amount of terminal alkyne under basic conditions to give a family of copper(I) alkynyl compounds [Cu(P3)CuCR]. The number of terminal –CuCH groups in the starting ligand determines the nuclearity of the resulting complexes giving mono- (1, R = Ph; 2, R = C6H4OMe; 3, R = C6H4NO2; 4, R = C6H4CF3; 5, R = 2-pyridyl), di- (R = -(C6H4)n-, n = 1 (6), n = 2, (7), n = 3 (2)) and trinuclear complexes (9, R = 1,3,5-(C6H4)3-C6H3; 10, R = 1,3,5-(C6H4-4-C2C6H4)3-C6H3). In all the complexes the Cu(I) centers are found in a distorted tetrahedral environment that is achieved by tridentate coordination of the P3 ligand and σ-bonding to the alkynyl function. The crystal structures of 1, 3 and 5 were estimated by single crystal X-ray diffraction analysis. The 31P, 1H and 1H–1H COSY NMR spectroscopy confirms that all the molecules remain intact in solution. The photophysical studies carried out in the solid state at 298 and 77 K revealed moderate to weak orange luminescence (Φem up to 19%), tentatively assigned to thermally activated delayed fluorescence for the mononuclear complexes. The quantum yields of emission of 1–10 demonstrated strong dependence on the nature of the alkynyl ligand, the role of which in the electronic transitions was elucidated by TD-DFT computational studies.
