57170-67-9Relevant academic research and scientific papers
Bulky monodentate biphenylarsine ligands: Synthesis and evaluation of their structure effects in the palladium-catalyzed Heck reaction
Quinteros, Gisela J.,Uberman, Paula M.,Martín, Sandra E.
, p. 2698 - 2705 (2015/04/27)
Biphenyl-based arsine ligands were prepared in two-step fashion by Pd-catalyzed arsination and microwave-assisted Suzuki-Miyaura coupling, providing sterically demanding arsine ligands in overall isolated yields up to 82 % as air-stable solids. Short reaction times were achieved with the assistance of microwave irradiation in the direct and simple described protocol for the synthesis of biarylarsine ligands. The activities of the biphenyl arsine ligands were explored in Pd-catalyzed Heck coupling. As a general trend, the ligands with "blocked" ortho-positions on the non-arsine-containing ring of the biphenyl backbone performed more efficiently in the coupling reaction. This catalytic system allowed several interesting stilbenes to be obtained in very good yields. Sterically demanding biphenyl-based arsine ligands were prepared in high overall yields by microwave-assisted Suzuki-Miyaura coupling. The ligands were evaluated in the Pd-catalyzed Heck coupling reaction; the most active were those with "blocked" ortho-positions on the non-arsine-containing ring of the biphenyl backbone.
Synthesis of biphenyl-based arsine ligands by Suzuki-Miyaura coupling and their application to Pd-catalyzed arsination
Uberman, Paula M.,Lanteri, Mario N.,Parajon Puenzo, Sol C.,Martin, Sandra E.
scheme or table, p. 9229 - 9237 (2011/11/05)
A versatile and efficient approach for the synthesis of new biphenyl-based arsine ligands, by a Pd-catalyzed arsination to introduce the -AsPh2 moiety, and then a Suzuki-Miyaura cross-coupling for biaryl construction is reported. By Pd-catalyzed arsination with n-Bu3SnAsPh2 (1), (2-bromophenyl)diphenylarsine (2, 83%) was obtained. The Suzuki-Miyaura reaction between the bromoarsine 2 and aryl boronic acids bearing different substituents provided biarylarsine ligands (80-99%). The efficiency of catalysts derived from the new biarylarsine ligands was evaluated in the Pd-catalyzed arsination with perfluoroalkyl iodides (RfI). Outstanding activities of catalysts derived from Pd/methoxybiarylarsine ligands were found in this coupling reaction affording perfluoroalkyl arsines in very good yields (57-100%).
Phosphides and Arsenides as Metal-Halogen Exchange Reagents. Part 2. Reactions with Aromatic Dihalides
Gillespie, Donal G.,Walker, Brian J.,Stevens, David,McAuliffe, Charles A.
, p. 1697 - 1703 (2007/10/02)
1,2-Dihalogenobenzenes react with two molar equivalents of lithium diphenylphosphide in the presence of furan to give, after oxidation, triphenylphosphine oxide (major) and the corresponding 2-halogenophenyldiphenylphosphine oxide.No trace of furan-dehydrobenzene adduct was observed in these reactions; however, 1- and 2-naphthyldiphenylphosphine oxides (9:4) were detected.These compounds were the major products from the reaction of the furan-dehydrobenzene adduct with diphenylphosphide, although the ratio of 1- to 2-isomers was quite different (1:9) in this case.Reaction of lithium diphenylphosphide with 3,4-dichloronitrobenzene gave tetrachloroazobenzene (40percent) as the only isolated product and attempts to replace 1,2-dihalogenobenzenes with 2-halogenobenzenediazonium salts gave much lower yields of products.Although dehydrobenzene is thought to be involved in many of these reactions, alternative mechanisms also operate, depending on the halides used.The reaction of lithium diphenylarsenide with 1,2-dihalogenobenzenes gave triphenylarsine as the major product and it seems likely that similar mechanisms to those involved in reactions of diphenylphosphide are operating.Surprisingly, dehydrobenzene-furan adduct reacted with diphenylarsenide to give naphthalene in high yield.
Carbonylvanadium, -manganese and -molybdenum Complexes of the Ligands o-C6H4EPh2(E'Ph2) (E, E' = P, As, Sb, Bi) and cis-Ph2PCH=CHPPh2
Talay, Ridvan,Rehder, Dieter
, p. 451 - 462 (2007/10/02)
The photo-induced reaction between the complexes (1), η5-C5H5V(CO)4 (2), η5-C5H5Mn(CO)3 (3) or η5-C5H5Mo(CO)3CH3 (4) and the ligands o-C6H4EPh2(E'Ph2) (E = E' = P: a; E = P, E' = As: b; E = E' = As: c; E = P, E' = Sb: d; E = P, E' = Bi: e; E = As, E' = Sb: f) and cis-Ph2PCH=CHPPh2 (g), L, yields - depending on the steric requirement of L - the compounds L ( = cis-V(CO)4(-), cis-CpV(CO)2, CpMn(CO), CpMo(CO)CH3; L = a, b, c, g), L ( = V(CO)5(-), L = d; = CpV(CO)3, L = d, e; = CpMn(CO)2, L = e) or mixtures of L and L (, = V(CO)4,5, L = e, f; , = CpV(CO)2,3, L = f).In the mono-substituted species L coordination (as indicated by the 51V NMR spectra) occurs through EPh2 and E'Ph2, which is explained by a reaction path via a lable chelate 5-ring structure.Shielding of the 51V nucleus decreases in the order g > SbPh2 > PPh2 > AsPh2 > BiPh2 (derivatives of 1) and g > SbPh2 > PPh2 > BiPh2 > AsPh2 (derivatives of 2), and is smaller in the rigid chelates incorporating the o-phenylene ligands than in the more flexible structures of phospha- and arsabutane complexes.This fact is discussed in terms of hindered ?-overlap due to distortion of the EVE angle, which also results in an increase of CO valence force constants in rigid chelates. 31P coordination shifts increase according to dppe a g and arphos b (dppe = Ph2P(CH2)2PPh2, arphos = Ph2As(CH2)2PPh2). 31P NMR spectra of the molybdenum complexes suggest that the basic geometry for 4a and 4b likely is tetragonal pyramidal, while the preferred structure for 4g appears to be the trigonal bipyramid with the ligand in equatorial positions.The crystal and molecular structure of 1a is reported.The complex crystallizes in the space group C2/c (a = 2196.0, b = 1080.1, c = 2022.7 pm, β = 124.6 deg).The most striking result is the small PVP angle of 80.8 (0.2) deg.Optimized methods for the synthesis of the ligands a-f are described; the ligands are characterized by their mass spectra. - Keywords: Carbonylphosphinevanadium, Vanadium-NMR; Phosphorus-NMR
