78557-92-3Relevant academic research and scientific papers
ALKYLARSINIDENKOMPLEXE UND ARSINIDENKOMPLEXE MIT VERSCHIEDENEN METALLEN
Sigwarth, Beate,Zsolnai, Laszlo,Scheidsteger, Olaf,Huttner, Gottfried
, p. 43 - 58 (1982)
The chloroarsinidene complexes (CO)5Cr As(Cl) Cr(CO)5 (I) and Cp(CO)2Mn As(Cl) Mn(CO)2Cp (III) react with R3Al (R=alkyl, aryl) to give (CO)5Cr As(R) Cr(CO)5 (II) and Cp(CO)2Mn As(R) Mn(CO)2Cp (IV), respectively.The alkylars
Halogen-Metal Exchange in Coordinated Halophosphanes: Synthesis of Phosphinidene Complexes
Lang, Heinrich,Mohr, Gerhard,Scheidsteger, Olaf,Huttner, Gottfried
, p. 574 - 596 (2007/10/02)
Coordination compounds of halophosphanes such as (R)(Hal)2P-MLn (MLn = Cr(CO)5, 1; MnCp(CO)2, 2; Fe(CO)4, 4) or (R)2(Hal)P-MLn (MLn = MnCp(CO)2, 3) react with R'Li species in various different ways; Reaction of 2 with R'Li (R' = CH3, n-C4H9) yields the substitution products 5, (R)(R')2P-MnCp(CO)2. 3 reacts with t-C4H9Li/TMEDA to give -Li+, 6, by lithium-halide exchange.The salts 6 are characterized by their reactions with various electrophiles leading to compounds 7, (R)2(R')P-MnCp(CO)2 with R' = H, D, Alkyl, (CH3)3Si, (CH3)3Sn.The salts 6 are also obtained by deprotonation of 7a (R' = H) with n-C4H9Li. - Compounds (Aryl)(Hal)2P-MnCp(CO)2, 2j-m, react with t-C4H9Li/TMEDA to produce deeply coloured phosphinidene complexes R-P2, 10, in yields up to 80percent.Analogously, (Ph)(Cl)2As-MnCp(CO)2 gives the arsinidene compound Ph-As2 (11) in 90percent yield.Whereas 11 had already been known, the compounds 10 are rare examples of phosphinidene complexes containing an R-P ligand bridging the two 16-electron fragments MnCp(CO)2.The phosphanediyl ligand is stabilized by metal-d?-phosphorous-p? interactions with the phosphorous atom in a trigonally planar environment.The unconventional bonding situation in 10 is evident from the electron spectra as well as from the 31P NMR shifts, which range up to 896 ppm.
Arsiniden-Komplexe: Synthesen, Substitutionsreaktionen, Spektren und Strukturen von XAs5Cr>2 und XAs5-C5H5(CO)2Mn>2 (X = Aryl, Halogen, RE mit E = O, S, Se)
Seyerl, Joachim von,Sigwarth, Beate,Schmid, Hans-Georg,Mohr, Gerhard,Frank,Albin,et al.
, p. 1392 - 1406 (2007/10/02)
Within the arsinidene complex ClAs2 (1a) the chlorine function may be substituted by reaction with nucleophiles such as halide ions, alcohols or their S- and Se-homologues by other halogens, or RO-, RS- and RSe-groups, respectively.Phenyl substitution occurs with BiPh3 as the phenylating agent.Chlorine-bromine exchange is observed upon reaction of 1a with BBr3.ClAs5-C5H5(CO)2Mn>2 (2a) behaves similarly to 1a.For the synthesis of phenylarsinidene complexes other methods in addition to halogen substitution have been developed.The electronic spectra of the deeply coloured arsinidene complexes are discussed in context with the electronic spectra of phosphinidene and stibinidene complexes. - The structural chemistry of arsinidene complexes, which contain trigonally planar coordinated arsenic(+1), is exemplified by the X-ray results obtained from 1a and 2a as well as PhAs2 (1d) and PhAs5-C5H5(CO)2Mn>2 (2c).
